Lesson Plan in Classroom Program Essay

In our modern epoch, the time when the only things that are needed for effective learning are the teachers and students is long gone. At the turn of the millennium, the equation to successful teaching also has the variables of classroom schedule, room assignment and even proper assignment of teachers. Although these factors may seem insignificant, all of those can be the telling elements as to whether the highest possible level of edification is attained. During our first teaching episode in our cooperating school, Tagum City National Comprehensive High School, I quickly took notice about the schedule of our CT. Mam Mercado’s schedule is obviously loaded, with only a few minutes of break or rest in between. Her class schedule as well as room assignment was relatively reasonable (in the Philippines’s educational setting). As she is assigned to teach English which is her major, it can be concluded that her students will acquire adequate learning. All these factors greatly contribute to the effectiveness of teaching as well as learning. Having stated that, I realized that for a lesson or a curriculum will be best implemented and taught if all the necessary components, which in this case are the class program, teacher’s assignment and room assignment, are present and well organized. Proper organization can greatly influence and even pad up the interest and enthusiasm of the students. On the part of the teacher, it eases up the tasks to be done knowing that most of these portions which he/she can’t control are put right in place. With that considered, the educational institution can be confident that the zenith of the teaching-leaning process is achieved. Due to some obvious reasons, we were not able to interview our CT about her Class Program. However, she shared to us how important it is to prepare a class program and implement it adaptably. With that, both the teacher and  the learners will know what to do expect as well as do next. With all that has been learned, I realized that there are many dynamics to be considered before effective edification can be professed. Most importantly, proper preparation and implementation of the class program should be given due concern for it can immensely affect learning.

Dorothy and the Tree Essay

Dorothy and the Tree: A Lesson in Epistemology Stanley Fish discusses how we in society base our lives off of assumptions. Using the example of Dorothy and the tree, Fish is able to show how with our assumptions, we as people categorize others and things into what we believe to be correct. Whether or not we have actually taken the time to figure out if we are right is irrelevant. He notes that we should just â€Å"keep trying to expand our sense of ‘us’ as far as we can†, so we can avoid judgments and isolating ourselves from the rest of society. Even though Dorothy realizes her mistake, she doesn’t realize that it is not a failure, but her consciousness assuming the classification of things in the world. Fish later on defines thought as the â€Å"structure that at once enables perception†, meaning that within categories things emerge, limiting perception and nothing can allow one to see everything because that is God’s job. Fish uses many Bible allusions to create justification for his assertions. He uses Genesis 1:26, and Paul’s road to Damascus to show that people can be persuaded to change their placement of things in society. Despite all of his valid points, Fish states that it is nearly impossible for one to change just on realizations. He believes it takes practice to accept the fact that there are things that we cannot comprehend because there is no limit on the conceptual trappings of society.

Research proposal- air pollution around london and child health Essay

Research proposal- air pollution around london and child health - Essay Example The data for use in the project will be in the form of both descriptive and inferential statistics while the analysis will employ both qualitative and quantitative methods. About academic and scholarly articles, industrial air pollution significantly affects children health. An analytical comparison of London and other non-industrial cities the world helps to establish the above statement. This project proposal aims at highlighting the neglected issue of industrial pollution on the health of city residents. This research proposal is about air pollution around London and child health. The research is therefore aimed at investigating the effects of air pollution and its significance on public health. Previous research has established air pollution in central London to affect all the people living and working in the English capital city. In 2008, statistics from the London Local Government estimated 4,000 deaths to be related to air pollution (KuÈnzli et. al, 2000) . Over the past 50 years, the U.K Government has made several significant steps towards the reduction of air pollution. However, the latest research findings have found children to be the most vulnerable age group alongside older people. Asthma the most familiar childhood chronic respiratory disorder is on the increase in London and other industrialized cities. In the 1980’s, childhood asthma’s prevalence shot up by approximately 40%. Several factors have been associated with asthma and other respiratory diseases. These factors include biological and environmental factors. Biological factors include one’s genetic composition and allergy reactions. Environmental factors include tobacco smoke, dust mites and air pollution. Previous studies have directly linked ozone and particulate forms of air pollution as the primary causes of asthma in children (KuÈnzli et al, 2000). Several organizations globally have recognized the damage

Alba Madonna - Raphael Essay Example | Topics and Well Written Essays - 2000 words

Alba Madonna - Raphael - Essay Example Raphael's Alba Madonna, painted circa 1510 and measuring 37.5 inches in diameter, is one of the most well known examples of biblical themed Renaissance art. One of the work's key compositional features is the artist's selection of a circular framework to surround his depiction of the biblical triad of Mary, the child St John and a baby Jesus. The circle, with its theoretical and symbolic links to notions of eternity is invested with significance in the Judeo-Christian belief system. Conversely, in ancient mythology the circle often represented a serpent from head to tail - tying in with the serpentine satanic figure of Christianity's Garden of Eden. Surrounded by the circle, as the baby Jesus was encased in her womb before birth, Mary is surrounded by a miasma of potent symbolic associations - including those of creation, rebirth and destruction. The foreground scenery of the piece is relatively barren, in contrast to the reproductive success of the virgin mother. In biblical ideolog y, it was a tragedy for a woman to be seen as barren - as traditional gender roles determined reproduction to be a woman's primary function. Conversely, a fertile woman was seen to be blessed by God. The emphasis on a barren landscape heightens the associations of fertility connected to the Madonna, and the barren scene is broken by the appearance of two flowers - symbolising qualities of purity in their whiteness and similarly reflecting the virginal purity of Christ's mother.

Should the Raelians be accepted or rejected as a true religion Essay

Should the Raelians be accepted or rejected as a true religion - Essay Example Thus it is something that we all humans can be said to have in common. However, there is a great number of varying religions today. Some religions believe in Jesus Christ, others believe in Allah, some believe in other gods and goddesses, and some believe in philosophy. As a social institution, religion is founded by a group of individuals who develop a set of common beliefs and morals as well as practices and reverence for the same things (Breaux, 2008). But what makes a religion a religion? Breaux (2008) identified five sociological characteristics of a religion. These characteristics are very important to the organization and prolongation of the religion. The first characteristic of religion is that it is composed of group of people (Breaux, 2008). In order for a religion to develop and continue, it must be shared by a group of individual that shares common belief, norms, and must be identified as one. The second characteristic of a religion is that there must be certain beliefs t hat make up the structure of the religion and are accepted and embraced by each member of the group (Breaux, 2008). The practices of the group are very important and considered the third important characteristic of a religion (Breaux, 2008). Every religion has patterns of practices that become norms and prescribed rites become rituals (Breaux, 2008).

Structure of an Organization of Bank of Canada Essay - 1

Structure of an Organization of Bank of Canada - Essay Example This paper illustrates that most of the organizations’ structure tends to be quite flexible and easy to manage for the day to day business. However, large organizations in majority of times become bureaucratic and tend not to be flexible enough in order to deal with the challenges of the contemporary day business. The most significant point to consider is that the structure of the organization needs to permit it to fulfill its objectives and also needs to ensure that the structure fits with the business environment in which it works. The range of organizational structures are the ‘entrepreneurial structures’, the ‘product-based structures’, the ‘function-based structures’, the ‘divisional structures’, the ‘matrix structures’, and the ‘holding company structures’. The bank is observed to present the financial services that are generally diversified in nature. The various business segments of the compa ny are wealth management, international banking, capital markets, Canadian banking and insurance. The chart presented below is the three-level organizational chart of Royal Bank of Canada. It can be stated that the board of RBC has an independent chairman. There are 16 directors who are associated with the organization independently and there are two executive directors. The term departmentalization can be understood as the process whereby the tasks are grouped into departments. Five basic methods of grouping the activities are followed; they are ‘departmentalization by-product, departmentalization by the process, departmentalization by customers, departmentalization by geographical regions and departmentalization by function’. In the organizational structure, it is the jobs that are the most significant factors. The primary managerial decision is job design in the organizing function. Those jobs are generally assigned to the individuals that consist of the objectives a s well as the specialized task of the organization. It is worth mentioning that the overall task of the organization cannot be assigned to a single person. For instance, the bank may consist of numerous individuals. However, it is not possible for the single individual to take the responsibility of the entire task. A few may take the responsibility of taking deposits while others may be assigned the task of the granting loans.

Employability in a Knowledge Essay Example | Topics and Well Written Essays - 1250 words

Employability in a Knowledge - Essay Example Now a days education is not only looked upon a very fulfilling profession but has also become very competitive and lucrative. Given my abilities and interest areas, I feel that I possess all the pre requisites that are considered essential to succeed in this line. I have always been passionate about teaching and interacting with children comes naturally to me. Through this noble profession I will not be making a living but also doing something for the society as a whole. In my own small way I will be responsible for shaping the future of the nation. This thought is one of the major driving forces for my passion towards teaching. Also I , as an individual, has this thirst for continuous learning and development thereby broadening my horizon and enhancing my knowledge. I feel that this profession would fulfill this need of mine as one of the major demands of teaching as a profession is to continuously upgrade your knowledge and to be in synch with the changes and developments happening at around you. There is a need to constantly keep yourself updated and enhance your skills and knowledge if you have to succeed in the line of education. In order to succeed in a career of ones choice is it absolutely critical to understand how one can stay employable irrespective of the economic scenario and labor market conditions. ... a profession , one only needs to have the requisite qualification and skills that are required to fulfill the demands and the requirements of the concerned job. This definition is incomplete because it does not take into consideration the relationship between employability and the prevalent economic scenario. The economic situation of any country tends to have a significant impact on the labor markets thereby affecting the employability of people. It is a true case of demand and supply. During times of labor shortages, even the unemployed will be able to get decent jobs and when there are shortages of jobs, the highly employable people also might find themselves without any job. Secondly employability of an individual does not only depend on his qualifications but also how competent he is as compared with others who are applying for similar positions.These two important dimensions are not acknowledged in the definition provided by Hillage and Pollard. Drawing from the above argument the definition of employability given by Brown et al is more comprehensive and takes into account all factors that have a significant impact on this concept of as well as highlighting those aspects which graduates must consider to ensure the success of their professional careers. Firstly according to Brown at al employability is not only dependent on individual characteristics rather it possesses two dimensions namely absolute and relative. Therefore employability among graduates not only is a function of skills and qualifications but also depends on the capability of an individual to find and maintain different kinds of employments.The second important concept of employability as defined by Philips Brown is with respect to positional competition. He is of the opinion that employability

Proposal Argument Essay Example | Topics and Well Written Essays - 750 words

Proposal Argument - Essay Example Indeed, such a twist of events has already been witnessed in Ohio in 2011 when a boy weighing two hundred pounds was taken away from his parental care and put in a rehabilitation home. Cleveland Weight authorities claimed the mother of the boy was putting the health of the boy at risk. The crucial question is whether parents should be held responsible for obese children. It is indisputable that the debate underlying the topic pertains to the question of nurture versus nature. Thus, in deciding whether parents should be held responsible for obese children, one should give considerations to the causes of obesity, questioning how large is the role of parents in making children obese. It is worth acknowledging that obesity is largely caused by dieting, among other factors that are informed by poor parental choices such as limited instillation for physical exercises in children lifestyles. Arguably, diet and lack of exercises are the major causes of obesity among children. Of all the abov e-mentioned factors, non-healthy eating is cited as the main cause of obesity, this is accounted for by the following reasons. According to Hellmich (56), people consume food without giving consideration to the number of calories in it. MacDonald’s meals comprise high amounts of calories that could, no doubt, result to obesity. For instance, Big Mac contains as significant as 500 calories, as well as 33 grams fat (Munger 1456). Even intriguing is the fact a large population of people are now consuming these kinds of foodstuffs. According to Hellmich (60), as significant as 80 percent of youths are overlooking the impact calories can have on their health by underestimating the amount of calories in their meals. This trend is attributable to the fact that many people prefer foodstuff with much sugar, fat and salt (Peta 34). During free times, many people would still opt to taking cookies and snacks. Besides that, most people watch television while eating these snacks. This crea tes a worrying situation since watching television fosters overeating. However, those opposed to the fact that parents should be held responsible for obesity of their children have asserted that there are various factors that cause obesity and which parents have no control over. This is particularly in reference to genetics. Indeed, according to Green and Hayakawa (503) genetic characteristics are considered to play an important role in triggering obesity incidences. Characteristics, such as high human appetite and slow rate at which a body carries out metabolic activities, are all determined by genes and as well as can be inherited. Under condition of food sufficiency, these two would work together and result in perfect obese conditions. Individuals found to consist of a gene associated with fat mass are considered more susceptible to obesity risks than those without the gene. Furthermore, obesity is associated with various syndromes, which are linked to genetic variations. These s yndromes include Prader Willi syndrome, Cohen Syndrome, Bardiet-Biedl Syndrome and MOMO syndromes. Of the People who experience obesity in their early ages, especially below ten, about seven percent contained one point of mutations in DNA. Studies have also pointed out that over eighty percent of children born to obese parents risked obesity by about 80 percent (Allison and Hayakawa, 506). Moreover, the hypothesis of the thrifty gene presupposes that

Summaries of two articles Essay Example | Topics and Well Written Essays - 250 words

Summaries of two articles - Essay Example The major influence on student learning and academic achievement are the children’s exposure to the quality of schools and teachers. A test based on the production function models was carried out on the quality of teachers and schools to explain their variance to a large extent on academic achievement rather than characteristics such as age, socioeconomic status and sex over which schools have little or no control over. As a result of the tests, governments have a responsibility to invest in quality learning levels by identifying the goods and services such as library resources, audiovisual equipment, different contacts and homework required and investing in them. Government resources on quality learning are weak and schools have control, but characters that the schools have little control such as preschool measures and out-of-school measures are the major effects on quality learning by schools(Little & Andy 168). Students from high income countries such as US practice preschool measures not influenced by the government or school control compared to low income countries which spend a lot of money on similar academic learning. Academic learning is of quality when it influences social achievement and students are not controlled by schools given their characteristics. The second article is on the importance of teaching as a career to first time tutors. It is necessary for any individual with an inspiration to become a teacher or enhance his or her teaching career to make an informed decision base. First time teaching requires proper understanding of the subject matter and the ability to recognize the learning needs of the students and, therefore, be able to engage them mutually according to their different learning capabilities in order to provide solutions for their success attainment and education progression. However, teaching poses numerous challenges for the first time teachers and, therefore, first time tutors should possess critical

Discuss this question(showing in the Details set) more likely to Essay

Discuss this question(showing in the Details set) more likely to discuss philosophy knowledge and opinions no source are needed) - Essay Example In this case, relativists are advocates of cultural tolerance. By holding that everything in the world is contains some relative truth and that all positions are equal, it can be concluded that the cultural aspect in the world is also among the equals. In this case, there is no culture that is superior or other that are inferior. By this, one can deduce that different culture defines the diversity of people. Similarly, all people have equality in all aspect and hence, the issue of cultural tolerance has its place in the relativist school of thought. Cultural tolerance refers to the situation where every person acknowledges and respects cultural diversity. As such, each cultural should be treated with dignity and equality. As per the definition, cultural diversity is all about equality of all people despite their cultural orientation. All this is hypothesized by relativists as they advocate for unconditional equality. In this case, we can conclude that the relativists universally are committed to cross-cultural

Buffalo, New York Essay Example for Free

Buffalo, New York Essay Nature, in its core function, is the cause and effect relationship offered to things with ascertainable objectivity, happening without cause. From this we can easily conclude that the state of the nature of something that something being an object with â€Å"thing-hood†, as humorously described in class is its beginning purpose and generality. There are a few debatable definitions of nature, which at first glance are very similar. On hand, we have nature that is described as the first, inchoate, thing belonging to it. To put in simply an objects nature is its core material for example, the nature of my Odd Future Fitted tee-shirt is Cotton. As well we have nature described as quote on quote the shape or look. This statement points to nature as the stereo-type or look of an object, for example, my MacBook does not have the nature of a MacBook unless it assumes the look of a generic looking MacBook. When looking at these definitions it is hard to find a large degree of difference as the stereo-typical MacBook is not only composed of parts generally used to construct a MacBook, but also its acceptance and appearance as a MacBook. For clarification we can use Aristotles example of a doctor healing himself. A artisan of medicine does not have the nature of a Healer, as that would imply that he attained this skill naturally, which is not true. For something to have nature said nature must come into being without cause. Therefor it is safe to assume that the Healer, whom is an artisan of medicine, is a Healer, but has the nature of a normal very day human. When speaking of nature Aristotle means the natures of particular things and would perhaps be better translated a nature a things. What causes differences amongst Laptops and people, even between two Healers? This can be answered by looking at chance. By chance variations are made upon things not to its nature, but to its physical or otherwise growth from its nature. For this reason we must assume that all things have a categorical nature, with variations to its structure. The term purpose can be applied to the science of nature because purpose is an integral part of nature its self. One can come to the conclusion that nature, being the first being thing-hood of an object, is parallel to its purpose by definition. Under these thoughts we inclusively described nature as the original cause or purpose of an object, with relation to its makeup, compositions and molecular materials. The grammatically correct sentence â€Å"Buffalo buffalo Buffalo buffalo buffalo buffalo Buffalo buffalo which means Buffalo New York bison, whom other Buffalo bison bully, themselves bully Buffalo New York Bison. This statement really speaks to the nature of words in the English language. Nature can be defined as living things in the natural world such as Animals, Humans, Plants, Protista, Fungus, and, various others. Theses thing are often associated with the natural world, one thing that is often called unnatural are the actions of humans, such as the making of plastic or unstable isotopes and mechanical constructs. Is it unnatural for humans to fly around in giant metal contraptions, is it natural to be able to cancel or postpone the effects of disease, is it unnatural to stop a potential pregnancy with just one pill, these are questions that one should ask when discussing the definition of nature or even human nature. According to the dictionarys definition of nature, humans are a part of nature. If this is true, then one can ascertain that all acts of the humans behaviors are quote on quote natural and will lead to natural consequences. What is the nature of humankind, many different philosophers during the renaissance have explored this thought. According to Wikipedia the distinguishing characteristics, including ways of thinking, feeling acting and reacting, that humans tend to have by their nature, independently of the influence of culture. In the eyes of Merriam-Webster human nature is the fundamental disposition and traits of humans, theories about the nature of humankind form a large part of every culture. It can be said that the nature of humans is that of a selfish, competitive, very social or altruistic. Some may even say that the true nature of humans is that of a selfish yet remarkably smart ape that is bent on destroying itself, or that they are the one true guardians of the planet earth, sent here by some unknown force to protect and safe guard for generations to come. Most people believe that humans were created by God, and can go through immense improvement if economical, and social conditions were reformed so that hunger, death, and disease could be wiped off the face of the earth. There are lots of people that would argue that nature of humans is innately bad. Looking throughout history there are a plethora of accounts in which humans have shown the less admirable side of our nature. It can be said that it is quite natural for humans to kill and degrade the lives of other human (it does happen on a regular bases). Humans in their natural state have a tendency for greed and selfish behavior, a need to satisfy their own wants and desires; which often comes at the expense of other living things, human or animal. Of course since Man is a part of nature, and there for all his action are natural, one can’t really say that these attributes are particularly good or bad they are natural.

Management Principles: The Latham Report

Management Principles: The Latham Report The Latham report (July 1994) commissioned by UK Gov, written by Sir Michael Latham was an influential report defining the construction industries failures, constraints and procedures. The report identifies construction projects from start to finish, including the understanding of professional rolls, contract variations to achieve best practices including procurement and contract mediation. Clients are understood as having a key role towards the speed of a construction project. Understanding the nature of the construction industry is said to be essential to gain a better understanding of how a project will proceed. Lathams report recommended that such tasks will also have to include legal advice from certified consultants such as the client representative. Areas such as notifiable projects, professionals, communication, declaration of roles and responsibilities, project frameworks, governing bodies, liability, design procurement should all be generally understood within a clients role. Contractors where greatly influenced by Sir Michael Latham recommendations, he said that the principles of communication between contractors within the construction industry are currently having a detrimental effect on site activities and costs. He thought private sectors should get together to establish a clients forum. Latham determined that a checklist of design responsibilities should be prepared in order to prevent confusion to determine the liability of a project team. Sir Michael Latham thought that the use of co-oridinated project information should be written into contracts as a legal requirement, Latham ultimately wanted contractors to communicate better between themselves in order to assist the prevention of delays in a construction project. The Latham report talks about the responsibility of building services and design. The report highlighted that contracts agreed between professionals should be defined in a clear and precise manner; he maintained that everyone involved within a construction project should be able to understand the context of their contracts. Design and build of a contract largely depends on the project involved. The Latham report states basic design decisions on procurement should precede the preparation of an (outlined) project brief, as any project brief will largely depend on procurement matters to actually determine the structure of a projects brief. Duties, Accountability and delegation are all highlighted in The Latham Report, simplifying the delegation of duties highlighting possible penalties within a consultants/employed role for a construction project. Sir Michael Latham interpreted construction founders and agencies such as the CIC (Construction Industry Council), ECA (Electrical Contractors Association), BEC (Federation of Master Builders) FMB to help increase awareness of duties, accountability and delegation. Principles of accountability should delegate rolls duties therefore determining liability and responsibility for a professional. Simply stating tasks like responsibilities and consequences to clients and in contracts will make a construction projects duties more defined and easier to determine, therefore contributing to a smoother process. Task 2 Pioneers of scientific management are considered to be H. Gannt, Lilian Gilbert and Frederick W. Taylor. The Later Scientific school theories are largely dependent of the works of these economists. They aimed to influence industrial production with their interpretation of strategy towards the running of a more productive business, in turn lowering production costs and increasing company profits. Frederick W. Taylor quotes Taylors work influenced the general deminer of a company increasing the motivation of a work force by identifying key aspects of the managerial process like, constant innovations being discovered through the efficient use of testing (time trial .e.g.), seeking more effective equipment to decrease workmans efforts and hopefully increase the longevity of production and implementing framework organisation such as University Power Points Contingency School is a trend of management stating there is no single way to manage, different approaches to management result in different results, therefore highlighting management as an area that can greatly vary between personal. Managers are faced with the task its self to determine the management involved, for example selecting a manager for a retail shop will be very different to selecting a manager of an oil rig. Contingency thinking helps not apply 1 best way to management; it will understand the situation in front of them and aim to apply an effective managerial approach to the selection and implementation of a manager and a mangers role. Contingency was developed from many theorists concurrently in the late 1960s, Max Webber 1846 -1920 Bureaucratic Management and Frederick Winslow Taylors Scientific Management where considered to be part of the founders of economic interpretation. Frederick W. Taylor sometimes called the father of management, was a leader of the efficiency movement toward economics. He published The Principles of Management in 1911 based on his own past experiences of management interrupted towards looking into more efficient management processes, Taylors interpretation of scientific management contained 4 principles: Management Culture: China And United Kingdom Management Culture: China And United Kingdom Introduction: In this essay we are going to compare the Chinese and UK approaches to organization management culture. Taking into consideration recent phenomenon, rapid growth rate of businesses in China, expanding and growing investment portfolios have made noticeably Chinese businesses meaning, and foreign investors wanting to set a business in China. Whats interesting is the Chinese have different style, attitude and negotiation process towards employees and organisation as to the UK. The essay will state the differences between organizations in both countries and to look at the cultural dimension of both the East and the West, taking into account the different managerial styles and most importantly culture, whilst comparing both countries. The issue of globalization slides across as the process has made businesses able to connect worldwide. In order to get a closer look, case-studies will be examined looking at companies from a Chinese and UK business perspective. Despite the differences, comp lexity, similarities or disadvantage of one model to another, the Chinese way of operating is interesting especially seeing the importance and link between the countrys culture, relationships and positions in management. China has been a great country in terms of great power, which also is one of the second largest economic in the world after USA and their businesses have been booming extravagantly and expanding as well. However, China has the highest current currency reserved in the world today. Management culture in the china and in UK has been slowly integrated with one another. The Chinese management culture has undergone a period of flooded to the West and returning to the East. However we are going to examine the main dimension of culture, how they relates to businesses in China and UK. Different management researchers all over the continent have focused to the traditional Chinese management culture, whose ideal is in human orientation, and behavioural cultivation by self-disp line. This essay will consider the overall differences between the management cultures of China and the UK. In doing so the essay will consider both the general differences in cultural considerations as well as specific considerations and concepts which are present in Chinese management styles and cultures and how they relate or contrast to elements of the UK management culture.(Dongshui Su2001) Culture: In general terms it is accepted that there is a link between national cultures and management cultures (Handy 1999 p196-197). Hofstede (1980) considered a model of national cultures based upon the following four elements: Individualist vs Collectivist Low vs High power distance Low vs High Uncertainty avoidance Feminine vs Masculine traits From a national cultural perspective Hofstede identified that those countries of the Anglo-Saxon block which include the UK tend to exhibit a profile based around individualistic behaviour, low power distance, middling uncertainty avoidance and a high degree of masculinity. In comparison Eastern cultures were seen as having a greater degree of collectivist behaviour, a middling power distance a high avoidance of uncertainty and a high level of masculinity. As such in comparing the two cultures one may consider that there is a general convergence in the ability of exhibiting masculine behaviour whist there is a much more distinct difference in attitudes on the scale of individualistic vs. collectivist style behaviour. Chinese managers strongly believe in order and traditional values. Thus, Chinese bosses precisely like to share task to teams or groups to work in collective effort to enhance Just In Time (JIT ), and help the employees to work together and learn from each other as well. Although there are some disadvantages to work as team or group delays business project, in the sense that some individual would be sluggish on their own task, and when its time for promotion or bonuses equal reward would be given. In general terms whilst not as diametrically opposed Chinese culture may be seen as representing a much higher adversity to risk taking than that of the Anglo-Saxon countries. This may be seen as represented by the national differences in attitudes towards savings with Chinese citizens saving four times that of their Western counterparts (Graham and Lam 2003). In considering the effects of individualist models against those of collectivist cultures this has an impact for the consideration of overall management culture for instance the manager in an individualistic culture such as the UK will have to consider getting the best out of those they manage by aligning the best interests of the employee and the company from the individualistic perspective of the employee. For instance a popular way of rewarding employees in the UK is through a bonus culture in which the individual stands to benefit personally by meeting the needs of the organisation a theory which is largely embodied by Vrooms expectancy theory (Robbins 2007). In contrast management culture in a more collective society such as that of China may be seen as being able to appeal to the nature of employees to contribute towards the wider good of the organisation for which they have a greater sense of belonging to as a community than their UK counterparts. As such managers in such a cu lture may focus on giving praise and public recognition to employees with in the company before considering the need to use an extrinsic reward as a method of motivation. In addition the overall level of risk aversion within the national culture may be seen as translating into a model of management cultural and organisational behaviour. In many instances managers in the less risk averse countries of the Anglo-Saxon model are rewarded by shareholders for making what may be seen as risky short term profits and thus from the management culture perspective such a culture permeates every level of the organisation. On the other hand those operating in a more risk averse society such as that of China may be seen as being rewarded for acting in a way which is much more conservative with an emphasis on long term stability and profitability rather than short term share based performance. As such this adds to the general slower pace of business within Chinese cultures as personified by the general longer length of time taken in negotiations within China as opposed to between Western businesses (Ambler et al 2009). In a recent interview by Yi Min a director of Le nova Group in Carolina, he points out that collectivistic culture is less in China, since the late 1990s when the one child policy came into effect. These individuals born after 1980 ba ling hou are much more individualistic than collectivistic. Management styles and human behaviours: In many ways it may be considered somewhat difficult to generalise on the differences between management styles in the UK and China given that management styles are not necessarily related to an individual national culture but further segmented down to the corporate level. For instance even solely within the UK there may be seen as a significant array of management styles and cultures from the more formal and hierarchical in public services and more traditional business through to the informal and flatter organisational behaviour exhibited in more contemporary business such as a management consultancy businesses or a software producer. As such this section will now consider specific differences which may be used to explain potential differences in management culture which are specific at the national level rather than the organisational. Face One key consideration which may be seen as affecting the overall management style between Chinese and UK businesses is the concept of face. Within the overall Chinese culture there is the need for relationships, transactions and events to portray those involved in a positive light. As such in Chinese management styles both the leader and the follower must consider carefully what impact their actions have on the reputation of those they are interacting with. This may lead to a generally much more formal style of management in which leaders and employees take particular care to respect the boundaries and roles of those involved. Graham and Lam (2003) note that transactions between Western and Chinese companies can often fail due to a lack of respect for such formalities in which the Western company often issues a call me Mary approach thus not respecting a seemingly small but significant cultural consideration. For the Chinese business this also presents significant problems internally , for instance there may be the need for a junior member of staff to point out an operational issue for which there is a ready solution however in brining the problem the attention of a superior this may be seen as providing a conflict for the employee who may consider whether or not such an action will make his supervisor lose face. The Chinese prefer a more structural form and hierarchy followed way although much of this comes from the Confucian culture, which stresses the importance of social hierarchy, groups and positions. Empowerment: Organisations in the UK and the West believe in empowering its employees contrary to the Chinese, whom believe that when the task is not done, their boss would blame them. Chinese people do not like to be blamed. They prefer to be responsible for the work they handle themselves rather than to be empoweredto take on something new because of the fear of failure. Furthermore, if the Chinese managers apply the system of empowering subordinates , middle workers keep getting cut in organisations and somebody has to take up the task that used to be done there. The key for leaders would be to look for the right balance between empowering and doing the work themselves. As such a cultural concept can thus lead to a management style which encourages overall poorer organisational performance as performance suffers at the consideration of relationships. There is the consideration that in the UKs culture such considerations do not feature so widely and as such managers and followers are able to be much more frank about operational issues without considering a criticism of process or procedure to be a personal affront against the person responsible for it.. Chinese family businesses Another consideration in the concept of management style is that of the Chinese family business. Commentators highlight the fact that the structural form of a business will often have an impact on the cultural elements of the business (Johnson et 2008, Robins 2007) as such given the wide spread nature of the Chinese family business model this must be taken into account. Research suggests that to a large extent business in China is internalised into family groups a model which although suppressed under communism has re-emerged after the liberalisation from the smallest business to the largest conglomerate (Chen 2001). However the family business model goes beyond that of ownership as paraphrased by the consideration of the phrase family first, business second (Chen 2001 p20). This presents a key cultural difference between in cultural approaches to the running of a business between those in China and the UK. In the UK one may see that culture largely compartmentalises life bringing a clear separation between ones personal family interests and ones work or careers interests. On the other hand the Chinese family business model suggests that work and business life represent an extension of the family rather than a separate activity as in the UK model. This has major implications for management style and culture as one has to consider that under the Chinese family business model individual traits of families and their relationships will carry over into business practises as such Chinese businesses following the family business model may have a propensity to exhibit a greater level of paternalistic style of management as embodied in the family relationship than under UK models of business ownership. Process Another consideration is that there is a fundamental cultural difference between Chinese and UK cultures in regard to what is important when considering the issues of process and results. UK culture and human behaviour may be seen as to a large extent as steeped in the utilitarian philosophy in which the overall focus has become that of the result. Ultimately the utilitarian philosophy states that the only consideration is that of result and that process or how one gets to that result is completely immaterial (Graafland 2007 p149-155, Velasquez 1998 p73). This is in stark contrast to Chinese culture which built upon the cultural values of Confucianism amongst other philosophies emphasises the importance of process rather than results (Graham and Lam 2003). Although these are cultural considerations the impact upon management styles is quite formidable, as such Western approaches towards management tend to focus on results and speed of transactions were as Chinese approaches tend to f ocus the overall quality of the experience. As such UK management culture many be seen as focusing on contracts and short term transactional results whilst Chinese management cultures may be seen ad focusing largely on the building of longer term relationships over a much longer period of time. Negotiations: Negotiations may be seen as one of the most important measures of difference between Chinese and UK management styles given that the negotiation between a company from each country will highlight the exact differences in cultural terms. This section will now consider a number of specific elements which may be seen as having various degrees of difference between the styles and cultures of both nations. Negotiation in the china is seen as very frustrating and complicated because of the Chinese business culture, the Western businessmen see it as vast different. When comparing to UK businessmen who are very direct and straight forward when negotiating with foreign investors or internal businessmen. when negotiating with the West, both parties would come to agreement, so that the goals are met in a shorter time. Its much more different in China, before doing a business you need to have a middleman Zhong Yong someone in the middle that would put you through during the negotiation with the people involved. Having a middle man is idealist in China and comes at a great advantage, the Zhong Yong helps to facilitate the business activity and might act as a sign or guarantee of confidence from the eastern negotiator Time scales In general terms having considered the cultural considerations in the previous section time scales would seem to be a significant area of cultural difference between UK and Chinese companies. In general terms UK companies and negotiators may be seen as placing a high value on speed of negotiation and getting a final contract signed representing a results based approach. Chinese culture on the other hand may be seen as fuelling an approach in which time is much less valued with negotiations taking much longer over a larger number of meeting in which the process and quality of the negotiating experience is considered as more important than the actual result in the form of a contract. The barriers to entry and business start up in developing countries like China could have a fringe on its management technique and negotiation. Barriers like high level of government intervention, cost, taxes, policies, regulations. In respect to time, a good comparison is shown by a World Bank business survey on how long it takes to start a business in China and in the West. It goes on to show that starting a business in China could take up to 35days and in the UK would take up to 7 days. These barriers to entry shy way foreign investors and migrant (labour).Making it increasingly difficult to work, understand and adapt to another environment. Although things are changing in China with the influence of globalisation. Another key factor for the Western negotiator is communication, if for example the people involved are of different cultures, there is likely to be some language barrier in their method of communication. In the case when two people communicate they rarely talk about the same subject, but different meaning is laid out by each persons own due to culture Herbig,(1997). In negotiating in China, the Western businessmen need to know that conflict might occur where an individual does not know how to behave in the meeting. For example Chinese people read meaning to human behaviour a lot; They sit upright when sitting in chair with both feet on the floor and find it rude to point out your feet at another person. Trust: A concept and perception that last with the Chinese Culture, the importance of trust when doing business in China is highly regarded. Chinese negotiators look out for this in the Western negotiator for example if you did not attend the same school with the person, you just do not know them enough for them to build strong trust right away. They believe first make friend and then do business . The Westerns usually operate in a different manner and are more direct and straight forward, willing to accept your word.(Europe Asia Company Directory 1998) Guanxi One of the key elements to consider in the process of negotiation with Chinese entities is the concept of Guanxi, in general terms Guanxi represents the element of personal connections (Graham and Lam 2003 p39). The concept may be likened largely to that of the Western concept of networking however there a number of fundamental differences in that UK networks often focus on immediate transactions between those in the network and the benefits of such a network are often expected to be honoured at the time such as in reciprocal trading agreements, X offers Y and expects Z to immediately respond with a reciprocal benefit. In the Chinese negotiation process there is the consideration that such networks are based upon much longer term considerations and that a party will give or receive a benefit but may not return or receive the benefit for a long period of time to come. For the Western negotiator this may present a confusing evaluation, on the one hand a negotiation may seem a poor one from a single transaction perspective however in reality the negotiator may have banked a significant level of capital for future use. On the other hand a negotiator may have got what they consider a good deal however the ignoring of reciprocating such a deal in the favour of the other party in future could leave the company in a position of significant difficulty further down the line. Globalisation: The increased level of economic integration or globalisation may be seen as the overall justification for the research into the subject of the differences between Chinese and Western approaches to management and organisational behaviour. Globalisation in the context of Chinese and UK cultures may be seen as coming from three key driving forces, firstly the consideration that many companies since Chinas integration into the wider economy have seen China as a key source of resources be this in form of cheap labour or commodities such as oil and minerals. Secondly there is the consideration that many businesses see China as not a source of materials for export but a market for further development of sales. Finally there is the consideration that China does not simply represent a market and supplier for Western companies but also that China also has its own companies which wish to trade with the West for the same reasons. As such all of these drivers of globalisation bring together a nee d for those involved to understand and negotiate with what at times may be seen as quite opposing sets of cultures. The process of globalisation may be seen as largely a two way process in regard to the changing and acceptance of management cultures. On the one hand those businesses that have undertaken ventures in China have had to adapt to local customs and cultures with those companies such as GM who have localised their management styles and cultures doing significantly better than those such as Ford who had moved into the Chinese market using standardised models (Graham and Lam 2003, Hutchings 2001). However China in its economic integration with the wider world has also had to make concessions which have had a large impact on cultural elements. For instance as part of Chinas ascension to the WTO the Chinese government has had to significantly make recognition of such elements as contracts and intellectual property. Given the unimportance of contracts within the Chinese business culture this may be seen as a key way in which Chinese culture has began to adapt to Western cultural models as muc h as Western companies have had to adapt to Chinese cultural models. A final consideration in that of the globalisation process is the role of the overseas Chinese, a natural characteristic of the Chinese psyche may be seen as the suspicion of foreigners (Graham and Lam 2003). As such the overseas Chinese populations often provide a useful set of intermediaries between two sets of differing cultures in which the on the Chinese side of the supply chain gain the ability to trade with a trusted individual whilst the Western side of the supply chain has an asset in the form of a person who understands the intricacies of both the UK and Chinese cultures. Conclusions: There are many conclusions that can be drawn from the research which has been carried out, in the first instance one can see a direct link between the elements of national culture and management culture for both the Chinese and UK models of management and organisation culture. This has a distinct positive implication for these who may be seen as being able to bridge the gap between these cultures such as the overseas Chinese who on the one hand do not generate the initial suspicion of foreigners which is endemic to the Chinese culture but on the other hand have a deeper understanding of the national culture and thus management culture of the country for which they have settled in, the UK in this case. Other conclusions are that despite the high level of differences between UK and Chinese cultural models there are many elements which although not exactly matching have to a greater or lesser extent a general fit for example the Chinese concept of Guanxi may whist not exactly fitting wi th the Western concept of networking dose none the less have a resonance which allows Western managers to adapt the model to understand the Chinese version. Finally one must consider the distinct difference between UK and Western models of management culture in relation to Chinese models, whist the essay has often used the Western and UK concepts of culture interchangeably given that the UK may be seen as representing the West there are subtle differences when specifically considering the UK in comparison especially with the US version of the concepts considered. In many respects UK management culture may be seen as having a greater chance of success in adapting to Chinese models of management culture than that of the US for reasons which may be seen as owing to historical cultural considerations. For example whist there has been a link draw between the concept of networking and Guanxi the British concept of the old boys network may be seen as even more aligned to the concept than that of the original networking consideration. In addition the general British concept of gentlemanly conduct and a slower pace of life may also be seen as pro viding a greater resonance between Chinese and UK management cultures in comparison to the wider concept of Western comparisons.

Organopalladium Reagents and Intermediates

Organopalladium Reagents and Intermediates Joà £o T. V. Matos Table of contents Table of contents 1. Introduction 2. Organopalladium reagents and intermediates 2.1. The characteristic features for the use of palladium in organometallic chemistry 2.1.1. Oxidation States of Palladium 2.2. Preparation of organopalladium reagents and intermediates 2.2.1. Ï€-Ally Palladium Complexes 2.2.2. Cyclic aryl palladium complexes 2.2.3. Palladium Olefin and Diene Complexes 2.2.4. Palladium-TV-Heterocyclic Carbene Complexes 2.3. Methods for structural characterisation of organopalladium reagents 2.3.1. Nuclear Magnetic Resonance Spectroscopy 2.3.2. Infrared spectroscopy 2.3.3. X-Ray crystallography 3. Applications of palladium-catalysed organic reactions 3.1. Palladium-catalysed carbon-carbon cross coupling reactions 3.1.1. The Heck reaction 3.1.2. The Stille Reaction 3.1.3. The Suzuki reaction 3.1.4. The Negishi Reaction 3.1.5. The Sonogashira Reaction 3.1.6. The Tsuji–Trost Reaction 4. Final remarks Bibliography 1. Introduction Organometallic chemistry is discipline devoted to the study, not only of the compounds and intermediate species with metal-carbon bonds, but also the comprehensive study of all transformations and interaction between organic molecules and a inorganic metal from the main groups, transition series, lanthanides and actinides (Astruc, 2007; Crabtree, 2005). This interface discipline, between classical organic chemistry, coordination chemistry and inorganic chemistry, has proved, in the last decades, very useful to provide some important conceptual insights, new structures, and catalysts for different applications areas of organic synthesis, both in the academic and in the industrial fields (Crabtree, 2005). Organometallic chemistry also began to have a major impact on other areas such as: biochemistry with the discovery of enzymes that carry out organometallic catalysis; chemistry of materials due to the proprieties of some organometallic compounds to be used was precursors for depositin g materials on various substrates via thermal decomposition of the metal compound; nanoscience and nanotechnology due to the proprieties of some organometallic compounds to be used precursors for nanoparticles; and green chemistry by minimizing both energy use and chemical waste of several organic synthesis (Crabtree, 2005). The first organometallic substance to be prepared was synthesized in 1760, in a military pharmacy in Paris, by Louis Claude Cadet de Gassicourt. This French chemist, who was working on cobalt-containing inks, used arsenic-containing cobalt salts for their preparation. From this work was resulted the so-called â€Å"Cadet’s fuming liquid† which contains a mixture of tetramethyldiarsine and cacadoyl oxide (the first documented organometallic compound) by carrying out the following reaction (Equation (1)): (1) However, despise several organometallic compound discovered, along the eighteenth and nineteenth century’s, the truly â€Å"boom† of organometallic chemistry only occurred during the third quarter of the twenty century, in especially in countries like the United States of America, England and Germany (Astruc, 2007). One of the facts that contributed to this was the recognition of the potential of some d-block transition metals (i.e. nickel, palladium, platinum, rhodium, and ruthenium) organometallic reagents and intermediates as superior catalysts for new bond formation (i.e. carbon-carbon bonds) and their unique property to activate a wide range of organic molecules (Negishi, 2002; Schlosser, 2013). In this review, one of these d-block transition metals and their organometallic reagents based and intermediates will be put in broader perspective, the palladium. The use of this metal, has truly revolutionized the organic synthesis field over the last three decades, being nowadays, the most widely used element in organic synthesis (Crabtree, 2005). Probably the most notable example of its importance of the palladium intermediates as catalyst in organic synthesis is the attribution, by the Swedish Nobel Committee, of the 2010 Nobel Prize in Chemistry to Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki for their work in palladium-catalysed cross couplings in organic synthesis (Nobelprize.org, 2013). This review will attempt to highlight some of the outstanding properties of the organopalladium reagents and intermediates, identifying the main ways of preparation of these components, some of the most important analysis procedures to obtain their structural characterization, and prese nt some of the numerous applications and reactions where these compounds play an important role. 2. Organopalladium reagents and intermediates 2.1. The characteristic features for the use of palladium in organometallic chemistry Palladium is a chemical element discovered and isolated in 1803 by William Hyde Wollaston who named it after the asteroid Pallas, which was discovered a year before. Is a transition metal and belong to the 10th group, 5 period, and d-block of the periodic table. This atom, with atomic number of 46 and average atomic weight of 106.4 could occur naturally in seven isotopes, which includes six stable isotopes. Palladium, is nowadays one of the most versatile, selective, ubiquitous and significant metals used for organic synthesis and had truly impacted this field in the last four decades (Negishi, 2002). This fact is mainly because no other transition metals can offer such versatile to the abundance of possibilities of carbon–carbon bond formation that the palladium reagents and intermediates can offer (Tsuji, 2004). Furthermore, despite the palladium complexes are, in several reactions, highly reactive are stable enough to be used as recyclable reagents and intermediates, in catalytic processes (Negishi, 2002). In this sense palladium-mediated processes have become essential in several applications, namely in the syntheses of natural products, polymers, agrochemicals, and pharmaceuticals (Caspi, 2008). Despite the palladium being a rare and very expensive noble metal, there are several characteristic features and chemical properties which make reactions involving palladium reagents and intermediates particularly suitable in organic synthesis. One of the most important characteristic feature appears to be its moderately large atomic size factor which contribute to the moderate stability of its compounds and their controlled but wide-ranging reactivity leading (Negishi, 2002; Tsuji, 2004). Furthermore, its moderated size associated with high d-electron count, and its relatively high electronegativity (2.20 and 1.57 in Pauling and Sanderson scales, respectively), classified this element as â€Å"soft† element, which makes it a real alternative to the more traditional and â€Å"hard† organometallic reagents, such as the magnesium (Grignard) and lithium compounds (Negishi, 2002). Other important characteristic features is the tolerance from the palladium reagents and inter mediates to several functional groups (i.e. carbonyl and hydroxy groups) and which means that the palladium-catalysed reactions can be carried out without protection of these functional groups (Tsuji, 2004). Furthermore, palladium reagents and intermediates have a low tendency to undergo one-electron or generate radical in the reaction processes, reducing the possibility of unwanted side reactions and making the palladium-catalysed reactions quite clean and selective. Finally, another important feature, especially in the green chemistry context is their lack of toxicity problems associated and therefore they do not require too many special handling cares (Negishi, 2002). 2.1.1. Oxidation States of Palladium The most common oxidation states of palladium are 0, +1, +2, +3, and +4 (Pd(0), Pd(I), Pd(II), Pd(III), and Pd(IV), respectively). The palladium oxidation states of +1, +2, +3, and +4 correspond to d9, d8, d7, and d6 electron configurations, respectively, as shown in Figure 1. Figure 1.Representative d electron configuration of Pd(I), Pd(II), Pd(III), and Pd(IV) oxidation states (based on reference (Mirica and Khusnutdinova, 2013)) The vast majority of palladium-catalysed reactions, until the beginning of the twentieth-one century, were only focused in the reactions involving Pd(0) and Pd(II) oxidation states, since Palladium strongly favours this two oxidation states (Mirica and Khusnutdinova, 2013; Negishi, 2002). Despite the bulk of the organopalladium literature is centered on the use of Pd(0) and Pd(II) oxidation states, already in 2002, in the Handbook of Organopalladium Chemistry for Organic Synthesis, Negishi point out that the utilization of other oxidation states (Pd(II), Pd(III), or Pd(IV)), although it is still very rare, could become o be very significant in the future (Negishi, 2002). More than ten years later, and with the rapid evolution in the organopalladium chemistry, complexes with palladium in these oxidation states, especially the Pd(IV), have demonstrated their potential and they improved significantly their role in organic synthesis. Although the development of Pd(IV) chemistry has just begun, this has already made possible the development of a number of significant new transformations. Pd(IV)-catalysed reactions usually show a high selectivity and synthetic robustness, and in almost all of them the use of catalysts are generated in situ from commercially available palladium salts, making them particularly attractive from the viewpoint of cost effectiveness (Muà ±iz, 2009). However, by comparison with the Pd(0), Pd(III), or Pd(IV), complexes of odd-electron Pd(I) and Pd(III) oxidation states are much less used. Yet, despite the study of this oxidation states remains in its infancy, Pd(I) complexes have already been employed as pre-catalysts in organic synthesis (Canty, 2011) and despite the potential role of Pd(III) intermediates in catalysis is currently more speculative, this subject beginning to emerge considerable interest, as can be highlighted by the different articles and reviews on the subject (Canty, 2011; Mirica and Khusnutdinova, 2013; Powers and Ritter, 2011). 2.2. Preparation of organopalladium reagents and intermediates In the majority of the organic reactions that use palladium as catalyst, the organopalladium species are generated in situ during the course of the reaction, instead of a preparation of stoichiometric organopalladium reagents, ensuring that only a catalytic amount of palladium is used. In these cases, the reaction mechanisms should include a step were the organopalladium species are formed, the steps in which the formed species react with other reagents to generate a particular product(s), and the step in which organopalladium species are regenerated in a catalytically active form (Carey and Sundberg, 2007). There are several types of organopalladium intermediates extensively used in reactions with considerable importance in several synthetic applications. As reviewed by Schlosser (2013), more than 64000 entities with a palladium-carbon bond are known. Consequently, in this review, only the preparation of some of the most common organopalladium reagents and intermediates will be addressed. As special cares to have in the preparation of these complexes, palladium complexes, unlike the organometallics from the Group I and Group II, are not water sensitive. Consequently, in almost cases, strict exclusion of water is not necessary. Although, some reactions can beneficiate from the presence of water traces or can even be performed in water as solvent or co-solvent. Furthermore, palladium complexes could be quite to moderately air stable. Consequently, it is advised to conduct reactions using these complexes under an inert gas (i.e. argon or nitrogen) (Schlosser, 2013). 2.2.1. Ï€-Ally Palladium Complexes One of the most important organopalladium intermediates are Ï€-allyl complexes. The most common Ï€-allyl palladium complex, the dimer [(n3-C3H5)PdCl]2, was discovered more than 50 years, serves as starting material for a number of other complexes (Schlosser, 2013). Ï€-allyl complexes, can be synthesize from Pd(II) salts, allylic acetates, and other compounds with the potential of leaving groups in an allylic position, or can be prepared directly from alkenes by reaction with PdCl2 or Pd(O2CCF3)2. In this second scenario, the reaction occurs by electrophilic attack on the Ï€ electrons followed by loss of a proton, as represented in Scheme 1 (Carey and Sundberg, 2007). Scheme 1.Synthesize of Ï€-Ally Palladium Complexes by electrophilic attack on the Ï€ electrons (based on reference (Carey and Sundberg, 2007)). Due to the low electrophilic power, these complexes usually reacted with less-substituted allylic terminus of a variety of nucleophiles. After this reaction occurs, the resulting organopalladium intermediate breaks down by elimination of Pd(0) and H+, as described in Scheme 2 (Carey and Sundberg, 2007). Scheme 2.The overall transformation of the allylic substitution. (based on reference (Carey and Sundberg, 2007)). 2.2.2. Cyclic aryl palladium complexes Another important organopalladium intermediates are the cyclic aryl palladium complexes, or palladacycles (Schlosser, 2013). This complexes, are quite relevant role in cascade transformations leading to complex molecular architectures, in the proximally) directed arylation reactions, and in several intramolecular cross-coupling reactions (Beletskaya and Cheprakov, 2004). Palladacycles intermediates can easily be obtained by palladation reactions starting from Pd(II) salts and an arene having a directing group (Schlosser, 2013). Scheme 3.Palladacycles intermediates obtained by palladation reactions (R = NR2, PR2, etc., and Y = alkyl, aryl, etc.). Based on reference (Schlosser, 2013). In the cases where the directing group is an amine (e.g., benzyl or homobenzyl amines) or a phosphine (e.g., aryl phosphines), as represented in the Scheme 3A, the mechanism occurs by an electrophilic addition to the arene, and could include Pd(IV) intermediates. On the other hand, as represented in the Scheme 3B, Alkylarenes can also be substrates for palladacycles, in which, the activation of sp3-carbons next to an arene is presumably forced by agostic interactions (Schlosser, 2013). 2.2.3. Palladium Olefin and Diene Complexes The major group of organopalladium intermediates are the palladium Olefin and Diene Complexes. Pd(II) complexes having olefin ligands (i.e. 1,5-cyclooctadiene (COD), norbornene, or norbornadiene) can be obtained by reaction of Pd(II) chloride in the presence of the appropriate alkene (Carey and Sundberg, 2007; Schlosser, 2013). In this reaction the alkenes react with Pd(II) to give Ï€ complexes that are subject to nucleophilic attack. However, the products formed from the resulting intermediates are depending of the specific reaction conditions used. In the first case, represented in Scheme 4 as the path a, palladium can be replaced by hydrogen under reductive conditions. On the other hand, in the absence of a reducing agent occurs the obliteration of the Pd(0) and a proton, leading to the substitution of a vinyl hydrogen by the nucleophile, as represented in path b of the Scheme 4. (Carey and Sundberg, 2007). Scheme 4.Synthesize of the Palladium Olefin complexes. Based on reference (Carey and Sundberg, 2007). However, it is important to note that several of these palladium Olefin and Diene complexes are already commercially available (Schlosser, 2013). 2.2.4. Palladium-TV-Heterocyclic Carbene Complexes Palladium-TV-Heterocyclic Carbene (NHC) complexes have been recently introduced as powerful ligands for palladium. These NHC complexes have as main advantage the fact that they are quite stable, easy to handle, air-stable and can be easily be prepared from the ligand and palladium precursors (Chartoire et al., 2012; Schlosser, 2013). The NHC-based palladium complexes have been used very successfully for a series of different reactions, namely some cross-coupling reactions and aryl amination (Chartoire et al., 2012; Schlosser, 2013). In Figure 2 are shown some examples of these NHC-palladium catalysts, already used to ensure the efficiency of those reactions. Figure 2.Examples of NHC-palladium complexes: A) [Pd(NHC)(R-allyl)Cl] developed by Nolan; B) [Pd-PEPPSI-NHC] developed by Organ; and C) [Pd(IPr*)(cinnamyl)Cl] developed by Chartoire et al.. Figure adapted from the reference (Chartoire et al., 2012). 2.3. Methods for structural characterisation of organopalladium reagents The identification and structural characterization of the organopalladium reagents and intermediates, is of utmost importance in organic synthesis field, to understand the behaviour and proprieties of these compounds. However, it can be quite challenging and somewhat tricky task to accomplish. To achieve the identification and structural characterization of the organopalladium reagents and intermediates, the main analytical methods used rely on the complementarity of information provide from spectroscopic and crystallographic techniques, such as multinuclear nuclear magnetic resonance (NMR) spectroscopy, infrared spectroscopy, and x-ray crystallography. 2.3.1. Nuclear Magnetic Resonance Spectroscopy Multinuclear NMR spectroscopy is certainly the key methodology to elucidate molecular structures in solution. Consequently, just as has already happened in organic chemistry or biochemistry, it is now routine to measure NMR spectra of diamagnetic organometallic and coordination compounds. Nowadays, on a routine basis, organometallic chemists daily measure hundreds or even thousands NMR spectra, not only to identify and characterize the molecular structure of a given organometallic but also to verify if a reaction has taken place (Pregosin, 2012). The most investigated active nuclei in organometallic chemistry are, by far, 1H and 13C. However, there are several others readily measurable spin =  ½ nuclei, such as 15N, 19F and 31P, that provide structurally valuable chemical shifts and a diagnostic spin-spin coupling constants. Furthermore, often the measure of 1H and 13C NMR spectra alone may not be sufficient, especially when it is necessary understand the immediate environment of the metal canter and these probes are spaced apart from the metal (Pregosin, 2012). NMR is therefore widely applied for analysis to organopalladium reagents. For example, 1H NMR is the most reliable characterization technique which can be used on hydridopalladium complexes (Negishi, 2002). Moreover, there are several examples in the literature of the application of multinuclear NMR to organopalladium complexes (Leznoff et al., 1999; Paà ±ella et al., 2006; Satake et al., 2000; Schlosser, 2013). Even the 15N, and 31P NMR methodologies, are also are widely used in the characterization of organopalladium reagents, being possible to find studies in this field with more than thirty years (Motschi et al., 1979). 2.3.2. Infrared spectroscopy Infrared (IR) spectroscopy provides the spectral information corresponding to vibrational modes of a molecule. The position of the bands in the Infrared (IR) spectrum depends mainly of the on the strength of the bond(s) involved as measured and the reduced mass of the system calculated using the atomic weights of the atoms involved in the molecule (Crabtree, 2005). Consequently, IR spectroscopic are very useful to obtain a fast confirmation of the presence of some functional groups (i.e. C=O, C=N). However, this method should not be used as a sole characterization technique, since, for example, although the hydride ligands from the hydridopalladium complexes are expected to have Ï…(Pd-H) stretches occurring in the distinctive region of 1950–2060 cm-1 in the infrared spectrum, they are often very weak signals and are also rather dependent on the trans effect of the opposite ligand (Negishi, 2002). 2.3.3. X-Ray crystallography The structural characterization in the solid state, namely that provided by X-ray crystallography is an extremely important part of organometallic chemistry. In the method, a beam of monochromatic X-rays pass through a single crystal of the sample. Consequently, this beam is diffracted in the crystal in various angles, providing in photography the pattern of the crystal spots. The intensity of this set of diffracted beams will depend on the nature and arrangement of the atoms in the unit cell. Thus, the intensities provide the information about the locations of the atoms in the unit cell, while the relative positions of the spots on the photography film carry the information about the arrangement of the unit cells in space (Negishi, 2002). The results of an X-ray structural determination should be represented as a diagram showing the positions of all the atoms in the molecule, as represented in the Figure 3 for two different organopalladium complex (i.e.{Pd[(p-(Noxyl-tert-butylamino- 2-)phenyl)diphenylphosphine]2Cl2}, and{(ÃŽ ·-C3H5)Pd [(p-(Noxyl-tert-butylamino-2-)phenyl)diphenylphosphine](Cl)}) (Leznoff et al., 1999). Figure 3.A typical X-ray crystallographic characterisation of two different organopalladium complex (from the reference (Leznoff et al., 1999)) However, in addition to being assured that organometallic compounds (i.e. organopalladium complex) allow the growth of crystals to be used in this technique, there are some limitations than need to be overcome. First of all, since the X-ray diffraction results are usually based on one only crystal, is necessary to ensure that this crystal is representative of the bulk and free of impurities. One way to check that each crystal is the same material as the bulk of the sample is using the information from the IR spectrum. Furthermore, it is necessary to ensure that the solid state is really the same as the structure of the same material in solution, since several organometallic complexes exist as one isomer in solution but as another in the solid state. This point is especially relevant when the solid state X-ray results are compared with the solution NMR data. Again, in this aspect IR spectroscopy can be also very useful because we can obtain a spectrum both in solution and in the solid state, which emphasizes the need for the information complementarity of these characterization techniques (Negishi, 2002). 3. Applications of palladium-catalysed organic reactions As already pointed out, since the second half of the twenty century, palladium had increased its relevance and role in organic chemistry, in particular in metal-catalysed reactions. Palladium, together with some other transition metals, have the unique property to activate a wide range of organic molecules and thus to catalyse various bond formations. This metal, by far is the most commonly used metal, is thus of utmost importance in a wide range of applications, not only in academic circles but also in industry (Schlosser, 2013). An example of this application is the Wacker process. This reaction, discovered in the 1960s, uses catalytic amounts of palladium to oxidize ethylene to acetaldehyde, and is still widely used in industrial applications (in 2007, was generating four million tons of acetaldehyde per year (Astruc, 2007)). Another factor that has emphasized the importance of using palladium as a catalyst of organic reactions in academic and industrial applications was the introduction of several palladium-catalysed carbon-carbon cross coupling reactions. This fact can easily be verified by more than 200 natural products and biologically active molecules synthesized making use of the Heck reaction (section 3.1.1) and the â€Å"ton scale† fine chemicals produced in the industry using the Suzuki reaction (section 3.1.3) (Schlosser, 2013). Furthermore, these reactions also allowed the total syntheses of molecules used in the in the production of several medical drugs such as Naproxen (anti-inflammatory drug), Taxol (anti-cancer drug), (Z)-tamoxifen (anti-cancer drug), and morphine (Carey and Sundberg, 2007; Schlosser, 2013). 3.1. Palladium-catalysed carbon-carbon cross coupling reactions The introduction, in the last quarter of the twenty century, of palladium as catalyst in carbon-carbon cross coupling reactions, a new paradigm for carbon–carbon bond formation has emerged allowing the assembly of highly complex molecular structures and completely changed how the chemical synthesis is performed (Nicolaou et al., 2005). The capability of this reactions to forge carbon–carbon bonds between or within functionalized and sensitive substrates have received an enormous amount of attention among the synthetic chemists, and their scope has been very significantly expanded during the last several years, not only in not only in total synthesis but also in medicinal, biology and nanotechnology (Nicolaou et al., 2005). In general, the palladium-catalysed carbon-carbon cross coupling reactions can be represented by the Scheme 5. However, in this equation, for any given combination of R1 and R2, several parameters should be changed or optimized, namely the metal countercation M, the leaving group X, the palladium catalyst, the introduction of some additives or co-catalysts, the solvent, and even others parameters such as temperature, time, concentration, and mode of addition (Schlosser, 2013). Scheme 5.Geral model of the palladium-catalysed carbon-carbon cross coupling reactions (based on reference (Schlosser, 2013)). The characteristics of an ideal palladium-catalysed cross-coupling reaction can be listed as follows (Schlosser, 2013): Varied and inexpensive methods to set up the coupling substrate functionality from commercially available starting materials Easily activated high-yielding coupling under mild conditions; Generation of the minimal amount of by-product preferably by employing low-molecular-weight donors; Excellent functional group compatibility; General stability of the cross-coupling substrates; Low toxicity of precursors, substrates, and generated by-products. In this review, despite the extremely long list of all the possible carbon-carbon cross coupling reactions involving Palladium as catalyst, it will focus on the reactions that embody several of the above mention characteristics and are most commonly used namely, the Heck, Stille, Suzuki, Sonogashira, Tsuji–Trost, and the Negishi reactions. These reactions, have truly revolutionized the organic synthesis field (Nicolaou et al., 2005), and, as already mentioned, should be noted that the authors and works that gave birth to three of these reactions (Heck, Negishi, and Suzuki) were recently awarded the Nobel Prize in chemistry 2010 (Nobelprize.org, 2013), which emphasizes even more the importance of these reactions. 3.1.1. The Heck reaction The Heck cross coupling reaction has been developed independently by Mizoroki, (Mizoroki et al., 1971), and improved by Heck (Heck and Nolley, 1972) in the early seventies of the twentieth century. However, it took more than a decade for the potential of this reaction, be explored by the wider synthetic organic community, namely with the development of catalytic asymmetric Heck reactions (Nicolaou et al., 2005). The Heck reaction, as presented in Scheme 6, can be broadly defined as the palladium-catalysed coupling of a vinyl, aryl, benzyl halide or a trifluoromethanesulfonate (OTf) group with an olefin to yield products which result from the substitution of a the hydrogen atom in the olefin coupling partner (Nicolaou et al., 2005). Scheme 6.The overall mechanism of the Heck reaction (R4 = aryl, benzy

The Relationship between the People and the Land in Willa Cathers O Pi

The Relationship between the People and the Land in Willa Cather's O Pioneers       'For the first time, perhaps, since that land emerged from the waters of the geologic ages, a human face was set toward it with love and yearning' This quotation cuts straight to the heart of Willa Cather's whole argument throughout O Pioneers!, which is that it is Alexandra Bergson's will to survive and continually adapt which makes her successful -the facts that her neighbours are unwilling to take up new ideas and technologies, they are unwilling to gamble, and, worse, unwilling to listen to those whose relationship with the landscape is harmonious and respectful (such as that of Ivar), mark them down as part of the legacy of ignorant, unadventurous past. Alexandra is not content with a position such as Ivar's, though; she does not seek to subsume herself into nature, but to respectfully co-exist with it until she can in a greater development tame it. Whereas Ivar merely wishes to leave no mark, she has more controversial ideas. It is this which marks her out as something special; she was born with the fiery imagination of the true pioneer, born to prosper in "the struggle in which [she] was destined to succeed w hile so many men broke their hearts and died" (page 46). If she is so destined to succeed, she must similary be destined to make her mark on society of the time, on its established traditions, and sweep them aside in order for a brighter world vision to take their place.    There is overwhelming evidence presented by Cather for the inability of American society to coexist harmoniously with the individualist immigrant; they can accept only those who are willing to subscribe to the conformist doctrine ... ...ndra's face "there was that exalted serenity that sometimes came to her at moments of deep feeling." (page 170) She has 'clear eyes' (same page), with the inference being that she sees clearly now above all other times of realisation. It follows from her life and story that the land is a metaphor for nature, which is intrinsically bound up in the experience of human life.    BIBLIOGRAPHY: O Pioneers, Willa Cather, Oxford University Press, 1999. The Landscape and the Looking Glass: Willa Cather's Search for Value, John H. Randall III, Houghton Mifflin Company Boston, The Riverside Press Cambridge, 1960. FOOTNOTES: All quotes taken from the set text unless otherwise noted. 1. Back cover copy of O Pioneers! 2. Randall, page 68 3. Randall, page 291 4. Randall, page 20 5. Randall, page 72 6. Randall, page 67    The Relationship between the People and the Land in Willa Cather's O Pi The Relationship between the People and the Land in Willa Cather's O Pioneers       'For the first time, perhaps, since that land emerged from the waters of the geologic ages, a human face was set toward it with love and yearning' This quotation cuts straight to the heart of Willa Cather's whole argument throughout O Pioneers!, which is that it is Alexandra Bergson's will to survive and continually adapt which makes her successful -the facts that her neighbours are unwilling to take up new ideas and technologies, they are unwilling to gamble, and, worse, unwilling to listen to those whose relationship with the landscape is harmonious and respectful (such as that of Ivar), mark them down as part of the legacy of ignorant, unadventurous past. Alexandra is not content with a position such as Ivar's, though; she does not seek to subsume herself into nature, but to respectfully co-exist with it until she can in a greater development tame it. Whereas Ivar merely wishes to leave no mark, she has more controversial ideas. It is this which marks her out as something special; she was born with the fiery imagination of the true pioneer, born to prosper in "the struggle in which [she] was destined to succeed w hile so many men broke their hearts and died" (page 46). If she is so destined to succeed, she must similary be destined to make her mark on society of the time, on its established traditions, and sweep them aside in order for a brighter world vision to take their place.    There is overwhelming evidence presented by Cather for the inability of American society to coexist harmoniously with the individualist immigrant; they can accept only those who are willing to subscribe to the conformist doctrine ... ...ndra's face "there was that exalted serenity that sometimes came to her at moments of deep feeling." (page 170) She has 'clear eyes' (same page), with the inference being that she sees clearly now above all other times of realisation. It follows from her life and story that the land is a metaphor for nature, which is intrinsically bound up in the experience of human life.    BIBLIOGRAPHY: O Pioneers, Willa Cather, Oxford University Press, 1999. The Landscape and the Looking Glass: Willa Cather's Search for Value, John H. Randall III, Houghton Mifflin Company Boston, The Riverside Press Cambridge, 1960. FOOTNOTES: All quotes taken from the set text unless otherwise noted. 1. Back cover copy of O Pioneers! 2. Randall, page 68 3. Randall, page 291 4. Randall, page 20 5. Randall, page 72 6. Randall, page 67   

Modernizing Locke’s Natural Rights Essay -- Government

In Supreme Court Justice Thurgood Marshall’s article, â€Å"An African American’s Perspective on the Constitution†, he concedes that the founding father’s Constitution contained numerous imperfections. Marshall feels it was a product of time and tremendous courage that brought forth the fourteenth amendment to the Constitution, which guarantees an individual’s Lockean rights to â€Å"life, liberty and the pursuit of happiness†. Marshall believed the achievements that secured these individuals rights â€Å"belongs to those who refused to acquiesce in outdated notions† of life, liberty, and property. Thus, Marshall points out that the progression of time necessitates the modernization of the Constitution. Thomas Jefferson even anticipated the future evolution of our society and substituted the words â€Å"pursuit of happiness† for â€Å"property† in the Declaration of Independence having realized that someday our values would reshape. As public support for federal involvement has increased overtime, the Constitution is amended to better represent our evolving society. Although current public opinion favors federal support to provide access to healthcare, the design of our government dramatically lengthens the time necessary to implement modernize the Constitution. As the importance in maintaining one’s health has increased in America, the public has demanded the government to provide healthcare, however, the Constitutional prose recognizes the right to health but not the right to healthcare. The current escalating debt the federal government is accumulating to provide funding for programs like Medicaid is increasing the probability the United States will one day default on it’s debt. America’s primitive system of health care, known for its outstanding... ... Society. Washington, D.C.: Georgetown Univ. Pr., 1994. Faunce B.Med., Ph.D., Thomas. Who Own's Your Health: Medical Professionalism and the Market State. Baltimore, Maryland: The John Hopkins University Press, 2007. Marshall, Thurgood. â€Å"An African American’s Perspective on the Constitution† in Shafritz, [edited by] Jay M., and Lee S. Weinberg. Classics in American Government. 3rd ed. Belmont, CA: Wadsworth Publishing, 2006. The Declaration of Independence in Wilson, James Q., John J. Dilulio, and Meena Bose. 2011 American Government: Institutions & Policies. Boston, Mass: Wadsworth Pub. Co. Ruger, Jennifer Prah. Health and Social Justice. Oxford: Oxford University Press, USA, 2010. Wilson, James Q., John J. DiIulio, Jr., and with Meena Bose. American Government: Institutions & Policies. 12th ed. Boston, MA.: Wadsworth Publishing, 2011.

Review of Grahams Magazine Essay -- Literature History

Graham’s Lady’s and Gentleman’s Magazine (Graham’s) is a monthly published literary periodical although it allots other fields including engravings, fashion, and music to a small portion. This magazine deals with variety of literary fields from short stories, poetry, and essays handle various tastes from belles-lettres to sentimental literature. During those periods, the contributors to the magazine, in addition to numerous writers who exist only in tarnishing paper, are included such canonical writers as Henry Wadsworth Longfellow, Mrs. Lydia H. Sigourney, James Fenimore Cooper, Nathaniel Hawthorne, Edgar Allan Poe, among others. Through its inclusiveness in genres and wide range of literary works, Graham’s gained a broad readership, and simultaneously the magazine contributed to forging white American idealism by keeping silence on political or social issues at that time and reinforcing the already establish social system. This magazine’s silence for the contemporary issues is evident from its non-existent, editorial statement. One can hardly find explicit editorial position during 1843-44 for mainly two reasons. The owner and chief editor George R. Graham did not have his specific taste for literature or editorial position; his first concern was apparently a cultural business not culture itself. In his article â€Å"A Brief History of Graham Magazine,† Frank Luther Mott mentions that this magazine was the result of the combination of the Casket: Flowers of Literature, Wit and Sentiment and Burton’s Gentleman’s Magazine. He continues to contend that when Graham purchased the two magazines and merged as Graham Magazine, he just followed the merits from each magazine, which would promote the readership (364). On the other hand, Grah... ...ally have when opening a printed magazine. That is mainly because of the textual modes, microfilm or digitalized texts. When author’s works display in the screen in a small portion at a time, it produces another ahistorical text. This time one needs not draw one work from an anthology. Instead, the reader has to read the text confined by modern technology, which again alienates the text from the cultural or social atmosphere in the period when the magazine actually published. Works Cited Casper, Scott E., et al. A History of the Book in America. Vol. 3. The Industrial Book 1840-1880. Chapel Hill: UP of North Carolina, 2007. Print. â€Å"Editor’s Table.† Graham’s American Monthly Magazine 26.6 (1844): 296. Google Books. Web. 25 Sept. 2010. Mott, Frank Luther. â€Å"A Brief History of Graham’s Magazine.† Studies in Philosophy 25.3 (1928): 362-74. Web. 9 Oct. 2010.

Which Do You Prefer?

Every person has their own ways of living life. When an individual starts to make decisions, the quality of life is always considered. People resides in different parts of the world and the lifestyles varies from where they came from. Determining for the best place to live could give a greater impact in one's life as there are two options that are worthwhile to consider. For any reasons, an individual can freely choose the lifestyle of either in urban and rural living providing the advantages and disadvantages from both places. Urban and Rural settlements affects the lifestyle of a person as it differs from the kind of education, employment opportunities and the environment they live in. Education plays an important role to a successful career depending to the quality of education a person can acquire to learn. In rural areas, poverty is one of the main problems that affects the educational outcome of the students. This often leads to individuals dropping out school just to support and provide for their parents and to also help them manage the household. Moreover, not many children living in less developed villages have the opportunity to study, especially in college. Countless amounts of people may not have the opportunity to have the future they dreamed of due to the fact of where they grew up or certain circumstances in their life that disabled them from their goals. Distance is another problem have to face because of the lack of transportation. Although many struggle to get to places due to lack of transportation, those who live in the rural area struggle more. A teacher also faces many challenges in rural schools. Teachers in rural areas are paid with low salaries and the lack of teachers is another huge obstacle on the way to education. Teachers are extremely important because they give the students a foundation to work from and help the students build their way up in life. So the lack of teachers would make a huge impact on the students life and future. In urban areas, by contrast, an advantage manifested by urban students usually takes place in advanced country and economy. All of the students can get access of the wealth and social opportunities that big cities can offer. Urban schools are usually larger in size and they particularly have the resources and facilities that the rural area tends to lack. Most of the schools in the cities have advanced and qualified teachers as they get ahold of continuing trainings and workshops. The range of employment options must be considered when choosing a kind of job. In Urban areas where the population is high and extremely populated, most people intend to apply for jobs where they can get a good salary. According to the research from Public Use Microdata Area (PUMA), â€Å"the most high-skilled, high paying occupations tend to cluster in urban areas. Urban centers tend to specialize in knowledge-based work with high concerns of Technicians, Engineers, Scientist and Executives, while in rural areas have larger concentration of Machinist and Makers, which generally require less skill and receive lower salaries.† (Florida 2012).In rural areas, residents do not have enough employment options due to the lack of job opportunities and most people has an inverse relationship with agriculture. In contrary, urban areas are developed in an a planned and systematic way in terms of industrialisation. A division of labor is always present in the urban settlement for job allotment and because of the great opportunities for growth and the concentration of people, urban areas are preferred for developmental programs where the business are most likely invested. Environmental conditions gives an impact on an individual's quality of life. People living in remote places is usually described as a quiet and peaceful paradise which is a perfect place to unwind and escape from hustle and bustle of the city life. Besides rural areas are less crowded because there are not many people and cars. The scenery in rural areas are beautiful and well- conserved thus the people can enjoy the nature and have a peaceful mind. In contrast with the city dwellers, who lead a hectic life and often feel annoyed due to great stress in the daily life such as traffic, dealing with higher rates of crime and paying higher taxes. With regards to the nature, the trees are cut in urban areas for construction of roads and buildings that results to the lost of agricultural lands. The pollution and the deforestation has led to environmental imbalance and health problems, which shadow the future of urban living. Urban settlements are determined by the advanced conveniences, opportunities of education, facilities for transport, and business while the rural settlements are based more on natural resources and events. For a person who plans to reside on a specific place and get the kind of dream life however, will note the contrast between the settlement options along with how it differs in the quality of education, employment options, and the environment in both rural and urban areas.