Unexpected Halide Transfer: Aluminium and the Lanthanoids

Unexpected Halide Transfer: Aluminium and the Lanthanoids Unexpected Halide Transfer: Complex Reorganisation Between Aluminium and the Lanthanoids. Glen B. Deacon, David J. Evans and Peter C. Junk.* This submission was created using the RSC Communication Template (DO NOT DELETE THIS TEXT) (LINE INCLUDED FOR SPACING ONLY DO NOT DELETE THIS TEXT) [Pr(MeCN)9][AlCl4]3.MeCN undergoes reorganisation upon the addition of an ether. In the case of recrystallisation from tetrahydrofuran, the ionic nature is lost, whereas the addition of crown ether gives reorganisation, whilst maintaining ionic character. Isolation of homoleptic ionic trivalent lanthanoid complexes, under non aqueous conditions, has been investigated using nitrogen based ligand systems 1-5. The interest surrounding these homoleptic complexes is attributed to their potential catalytic properties 3,5. Under non aqueous conditions, the use of highly labile ligands, such as solvent molecules, presents the possibility of exposing the metal centre, hence providing a site for catalysis and thus can be considered to be ‘near naked 3. Complexes involving Ln3+ ions, that can be considered ‘near naked’ have to date been restricted to complexes such as [Ln(MeCN)n]3+ , with anions such as AsF6 and AlCl4 3-5. With this in mind, we have investigated the ability to access homoleptic ‘near naked’ Ln3+ complexes with tetrahydrofuran (thf) ligands. Currently, no such complexes have been reported for the smaller trivalent species unlike the larger divalent species, for which there is precedent viz. [Sm(thf)7][BPh4]2 6. Exploitation of the coordination abilities of crown ether has been investigated with the isolation of [ScCl2(18-crown-6)][FeCl4]. Via Sc n.m.r it has been shown that [ScCl(thf)(18-crown-6)][FeCl4]2 and then subsequently [Sc(thf)2(18-crown-6)][FeCl4]3 can be synthesised even though it has not been structurally characterised. With this in mind it should therefore be possible to isolate similar adducts in MeCN. Results and Discussion Homoleptic acetonitrile Ln3+ complexes can be obtained via two pathways viz equations 1 and 2 3. It was our intention to extend this chemistry to involve homoleptic Ln3+ complexes with ether ligands in place of MeCN. In reactions analogous to equations 1 and 2 with thf in place of MeCN, we found to our surprise [LnCl3(thf)2]n (Ln = Pr, Nd) was the sole Ln complex isolatable. This suggests that the complex is formed by a concerted process whereby AlCl4 binds to Ln3+ releasing AlCl3, allowing binding of another AlCl4 and so on until complete halide transfer to Ln3+ occurs yielding LnCl3(thf)n (equations 3, 4). Similarly, addition of 18-crown-6 to [Pr(MeCN)9][AlCl4]3 resulted in reorganisation to [(PrCl(à ¯Ã‚ Ã‚ ­Ã¢â‚¬â€œCl)(18-crown-6))2][AlCl4]2.2(MeCN) (1) † . Isolation of 1 illustrates there is an equilibrium in solution involving [Pr(MeCN)9][AlCl4]3.(MeCN). Conductivity measurements show a 1:3 electrolyte 7.This is in contrast to that previously reported for the Sm complex by Hu and supported by Bà ¼nzli for which a 1:2 is electrolyte is reported 4,8. We believe that the complex [Ln(MeCN)9][AlCl4]3.(MeCN) undergoes rearrangement in solution ranging from a 1:3 down to a 1:2 electrolyte (equation 5). This change in coordination environment of the lanthanoid metal establishes the pathway to halide transfer involving a transient species related to that shown in Figure 1. Structural motifs similar to this have been observed for several lanthanoid complexes including [Sm(ÃŽÂ ®6-C6Me6)(AlCl4)3] .toluene 9,10. The reaction is completed by the substitution of MeCN by the crown ether and cleavage of the bridging Al–Cl bonds in a similar fashion to that observed for reactions involving thf. Complex 1 has a nine coordinate Pr centre that is bound to all six oxygens of the crown ether. The Pr is also bound to one terminal and a bridging chloride, and dimerises through an inversion centre. There is a distinct change in bond lengths between the terminal (Pr-Clter 2.715(2)Ã…) and bridging chlorides (Pr-Clbr 2.839(2) and 2.858(2)Ã…) as would be expected with similar changes identified in [PrCl(à ¯Ã‚ Ã‚ ­-Cl)(tetraethyleneglycol)]2 11. The distances for Pr-Ocrown range from 2.572(4) 2.590(7)Ã…, following the same trends in the related cation [(DyCl(à ¯Ã‚ Ã‚ ­Ã¢â‚¬â€œCl)(dibenzo18-crown-6))2][(DyCl3(à ¯Ã‚ Ã‚ ­Ã¢â‚¬â€œCl)(MeCN))2] 12, albeit with a lengthening of Ln-O in line with increased ionic radius between Dy and Pr. The crown ethers adopt a saddle type morphology with the metal residing in almost the centre of the cavity made by the O1, O3, O4, O6 (0.601Ã…) plane and the O2, O5 (0.491Ã…) plane. The crown ether collapses to accommodate the smaller size of the Pr3+ which is evident in the planes derived by the oxygen atoms of the crown. The angle between plane 1 (O1, O2, O5, O6) and plane 2 (O2, O3, O4, O5) is 125.71o showing this slight closure to ensure that the oxygen atoms are all bound. This closure of the crown ether is observed for all the Ln3+ 18-crown-6 complexes in which the angle closes from 129.74o in complex [LaCl3(18-crown-6)] 13 through to 68.95o in [Lu(CH2(SiCH3))2(18-crown-6)][(CH2(SiCH3))B(C6H5)3].C2H4Cl2 14 owing to the reduction in size of the ionic radius of the Ln centre. Notes and references All reactions were carried out under dry nitrogen using dry box and standard Schlenk techniques. Solvents were dried by distillation from sodium wire/benzophenone (thf) or CaH/P2O5 (MeCN). IR and far IR data were obtained as described previously 15. Metal analyses were carried out by complexiometric EDTA titration with the addition of 5% sulphosalicylic acid to mask Al 16. Anhydrous AlCl3, LnCl3, and 18-crown-6 were supplied by Sigma Aldrich. AlCl3 was freshly sublimed prior to use. Conductivity measurements were carried out on a Crison Conductimeter 522 (serial no; 3807), using a locally manufactured air-sensitive cell. The complex [Pr(MeCN)9] [AlCl4]3 was made using previous published methods 3 and conductivity measurements were carried out as mentioned above (367.97 S cm2 mol-1 1.097 x 10-3 mol dm-3, MeCN). 1: Method A: [Pr(MeCN)9][AlCl4]3. MeCN (0.20g, 0.19 mmol) and 18-crown-6 (0.20g, 0.57 mmol), was dissolved in MeCN (30 ml). The solution was stirred and heated to near boiling to assist dissolution. The resulting green solution was then filtered and reduced in-vacuo. The solution was then cooled at -30oC yielding small green crystals. (0.21 g (81%)). m.p. 170oC(dec), C28H54Al2Cl12N2O12Pr2; calcd. Pr 10.27; found Pr 10.68%. I.r absorption (Nujol): cm-1. Unit cell collection confirms the same product as via method A. Method B: A mixture of PrCl3 (0.10 g, 0.40 mmol), AlCl3 (0.16 g, 1.20 mmol) and 18-crown-6 (0.29g, 0.83 mmol), was dissolved in MeCN (30 ml). The solution was stirred and heated to near boiling to assist dissolution. The resulting green solution was then filtered and reduced in-vacuo. The solution was then cooled at -30oC yielding small green crystals. (0.44 g (87%)). m.p. 170oC(dec), C28H54Al2Cl12N2O12Pr2; calcd. Pr 10.27; found Pr 10.42% I.r absorption (Nujol): 2291w, 2253s, 1644w, 1353s, 1291s, 1248s, 1082s, 1034s, 966s, 925w, 878w, 837s, 802w cm-1. 27Al nmr: 104 ppm(AlCl4) † X-ray data for complex 1 was collected on a Nonius Kappa CCD, MoKà ¯Ã‚ Ã‚ ¡ radiation,à ¯Ã¢â€š ¬Ã‚  Ãƒ ¯Ã‚ Ã‚ ¬ = 0.71073 Ã…, T = 123(2)K. The structure was solved and refined using the programs SHELXS-97 17 and SHELXL-97 18 respectively. The program X-Seed 19 was used as an interface to the SHELX programs, and to prepare the figures. 1: [(Pr(Cl2)(C12H24O6))2][AlCl4]2.2(C2H3N): C28H54Al2Cl12N2O12Pr2, M = 1371.91, green prismatic, 0.40 à ¯Ã¢â‚¬Å¡Ã‚ ´ 0.40 à ¯Ã¢â‚¬Å¡Ã‚ ´ 0.30 mm, monoclinic, space group P21/n (No. 14), a = 12.377(3), b = 15.356(3), c = 14.387(3) Ã…,à ¯Ã¢â€š ¬Ã‚  Ãƒ ¯Ã‚ Ã‚ ¢ = 107.97(3) °, V = 2601.0(9) Ã…3, Z = 2, Dc = 1.752 g/cm3, F000 = 1360, Nonius Kappa CCD, MoKà ¯Ã‚ Ã‚ ¡ radiation,à ¯Ã¢â€š ¬Ã‚  Ãƒ ¯Ã‚ Ã‚ ¬ = 0.71073 Ã…, T = 123(2)K, 2à ¯Ã‚ Ã‚ ±max = 56.6 º, 20600 reflections collected, 6215 unique (Rint = 0.0864). Final GooF = 1.022, R1 = 0.0478, wR2 = 0.1052, R indices based on 4182 reflections with I >2sigma(I) (refinement on F2), 263 parameters, 0 restraints. Lp and absorption corrections applied,à ¯Ã¢â€š ¬Ã‚  Ãƒ ¯Ã‚ Ã‚ ­ = 2.551 mm-1. Fig. 2 The structure of the cation [{PrCl(à ¯Ã‚ Ã‚ ­-Cl)(18C6)}2]2+. Hydrogen atoms omitted for clarity. Thermal ellipsoids shown at 35%. Coordination environment of the atom Pr(1) with applicable bond lengths (Ã…) and angles(o). Symmetry transformations used to generate equivalent atoms: -x+1,-y+1,-z+1. Pr(1) O(1), O(2), O(3), O(4), O(5), O(6), Cl(1), Cl(2), Cl(2), 2.572(4), 2.579(4), 2.574(3), 2.590(4), 2.588(4), 2.587(6), 2.715(2), 2.839(2), 2.858(2). Cl(1)-Pr(1)-Cl(2), Cl(2), 144.30(4), 143.18(4), Cl(2) Pr Cl(2),72.52(4). Fig.1 Proposed cation structure observed prior to ether coordination and subsequent cleavage of Al– Cl bonds. 1Evans, W. J.; Rabe, G. W.; Ziller, J. W. Inorg. Chem 1994, 33, 3072-3078. 2Willey, G. R.; Aris, D. R.; Errington, W. Inorg. Chim. Acta 2001, 318, 97-102. 3Deacon, G. B.; Gortler, B.; Junk, P. C.; Lork, E.; Mews, R.; Petersen, J.; Zemva, B. J. Chem. Soc.-Dalton Trans 1998, 3887-3891. 4Hu, J.-Y.; Shen, Q.; Jin, Z.-S. Chinese.Sci.Bull 1990, 35, 1090. 5Shen, Q.; Hu, J.-Y.; Jin, Z.-S.; Sun, J. Zhongguo Xitu Xuebao (J. Chinese Rare Earth Society) 1990, 8, 359. 6Evans, W. J.; Johnston, M. A.; Greci, M. A.; Gummersheimer, T. S.; Ziller, J. W. Polyhedron 2003, 22, 119-126. 7Geary, W. J. J. Coord. Chem. 1971, 7, 81. 8Bunzli, J.-C. G.; Milicic-Tang, A. Inorg. Chim. Acta 1996, 252, 221-228. 9Cotton, F. A.; Schwotzer, W. Organometallics 1987, 6, 1275. 10Cotton, F. A.; Schwotzer, W. J. Am. Chem. Soc. 1986, 108, 4657. 11Rodgers, R. D.; Henry, R. F. Acta Cryst. Sect. C 1992, 48, 1099. 12Rodgers, R. D.; Rollins, A. N.; Etzenhouser, R. D.; Voss, E. J.; Bauer, C. B. Inorg. Chem 1993, 32, 3451. 13Crisci, G.; Meyer, G. Z. Anorg. Allg. Chem. 1994, 620, 1023-1027. 14Arndt, S.; Spaniol, T. P.; Okauda, J. Chem. Commun. 2002, 896. 15Deacon, G. B.; Feng, T.; Junk, P. C.; Skelton, B. W.; Sobolev, A. N.; White, A. H. Aust. J. Chem. 1998, 51, 75-89. 16Schwarzenbach, G.; Flaschka, H. A. Complexometric titrations; 2nd English ; ed.; Methuen: London,, 1969. 17Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467. 18Sheldrick, G. M. Shelx97; A program for crystal structure refinement; release 97-2 ed.: Germany, 1997. 19Barbour, L. J. Supramol. Chem 2001, 1, 189. 1

Action plan for optimum health and wellness Essay

There are several elements of health and wellness, which include physical, social, environmental, emotional, spiritual, and intellectual. However, the top three elements of health and wellness that need more advocacy in society are physical, emotional, and environmental. Health is a good physical condition, the condition of the body and mind, and the presence of illness (Donatelle, 2011). Physical health is extremely important because exercise, for one, means the ability to have a strong, healthy heart, and good recuperating abilities. Incorporating different kinds of exercise into one’s daily routine will help not only relieve stress but also a variety of other health factors. Emotional health is a serious issue in our society today. Keeping a positive attitude and self- esteem is extremely essential for good health. When one lets certain situations fall to a low, it results in hurt, anger, and even depression, which are key factors of an unhealthy lifestyle. Possessing low emotional health could interfere with motivation to exercise, healthy eating habits, and good communication skills. Environmental health is also priority. Society can do certainly more to improve environmental conditions. This includes not littering, recycling properly, and less air pollution. These key elements ensure a positive clean way to healthy living. Understanding the important roles that nutrition and fitness have as active parts in our lives is a topic that requires additional advocacy. Nutrition and fitness are two key factors that work alongside each other and are critical elements that help maintain optimum health. Concentrations in good nutrition can deliver effective results in preventing the body from acquiring a chronic disease and obesity. Obtaining a chronic disease can have major impacts on a person’s life and requires extreme lifestyle changes. A chronic disease developed from poor nutrition is vital and can lead to many complications, inclu ding death. According to the CDC (2009), nearly one hundred and thirty-three million people live with at least one chronic disease. Consistency with daily exercise and good nutrition will ensure a healthy balance needed for good health and wellness. Without the right nutrition, fitness will not improve the body, and without fitness, nutrition will not have any additional benefits. Fitness is important because it helps fight infections in the body and improves the immune system to help fight infection at a more effective and rapid rate. Fitness is also important because it may give a person a sense of self-confidence. Self-confidence allows a person motivation and pride in who they are. Fitness will help primarily to live a better life in the way he or she thinks, sleeps, and in daily activity performances. It is mandatory to be consistent with eating healthy and staying fit. Great fitness and nutrition are necessities in obtaining optimum health and is achievable by incorporating daily physical activity. Without nutrition and fitness, a person will expose their body to a chronic disease that may eventually cause one’s life. Some of the environmental effects on health that people may be exposed to and be unaware of are in places such as the home and workplace, which can be fatal. Air pollution is one of the most common problems we encounter daily. Mold is another cause of concern with symptoms that range from something as harmless as a cough to a serious condition such as respiratory illness. Lead is one of the most significant and widespread environmental hazards for children. According to the CDC (2013), about 24 million homes in the United States contain deteriorated lead-based paint and elevated levels of lead-contaminated house dust. It is critical to know what environmental health hazards people can be in contact with in order to prevent any damage to our health. Other environmental issues people need awareness on is water contamination and toxic chemicals stored undernea th kitchen cabinets. The drinking water quality has a major influence on public health. Significant attention is required on all chemicals used in the home daily, which can be very harmful to one’s health if people use it inappropriately. It is particularly important to store toxic cleaning supplies appropriately when children are present in the home. In addition, smoking is an environmental health concern that can lead to very serious health problems, which includes the inhalation of secondhand smoke. Awareness of the resources and prevention  tips available is vital for all of these environmental health hazards. Making positive changes to the way the environment is today will ensure a healthier lifestyle. There are different strategies available for preventing chronic diseases such as cancer, diabetes, and cardio-vascular disease. First, one strategy for preventing cancer is maintaining yearly examinations at the physician’s office. It is also important to follow steps in checking oneself, more so, if cancer is hereditary. Proper nutrition is an import ant factor; however, there are specific items that can be included in daily eating habits, which will help in prevention. These items are green leafy vegetables and tomatoes. One should also avoid excessive sunlight and unnecessary x-rays for prevention of skin cancer. Exercising as often as possible to avoid stress is also a key factor for cancer prevention. Eliminating smoking habits and secondhand smoke are vital for prevention of lung cancer. According to the American Lung Association (2013), cigarette smoking is the number one cause of preventable disease and death worldwide. â€Å"Smoking-related diseases claim over 393,000 American lives each year† (American Lung Association, 2013). Diabetes best practices are staying away from drinking liquids that contain high levels of sugar. Walking, running or any type of physical activity at least twice a week is essential for keeping diabetes controlled. Cardiovascular disease is another chronic disease that is responsible for several heart attacks and deaths. Some helpful tips for prevention of cardiovascular disease are exercises such as walking o r running. The heart is a muscle; therefore, it requires physical activity to be healthy. Avoiding some red meats and incorporating healthy breakfast meals like oatmeal are also very helpful. There are several tips one can follow for prevention of cancer, diabetes, and cardiovascular disease. Staying proactive and aware of these issues is necessary to live a healthy life. â€Å"On the whole, the immune system does a remarkable job of defending you against disease-causing microorganisms† (How to boost your immune system, 2013). However, there are different factors that play a role that help attack the immune system, causing defenses to weaken. When germs invade the immune system, this causes one to get sick. Certain illnesses, such as diabetes, and AIDS can cause the immune system to not perform at an optimum level and allow sickness to invade the body more quickly. There are several ways to boost one’s immune system to achieve strong fighting  defenses. Good nutrition, proper vitamins and good exercise are some examples to boost the immune system. â€Å"To function well, it requires balance and harmony† (How to boost your immune system, 2013). Adopting healthy-living strategies is necessary to ensure good health, which means a strong immune system with strong defense fighting capabilities. â€Å"There is still much that researchers do not know about the intricacies and interconnectedness of the immune response† (How to boost your immune system, 2013). According to How to Boost Your Immune System (2013), â€Å"for now there are no scientifically proven direct links between lifestyle and enhanced immune function†. REFERENCES Centers for Disease Control and Prevention. (2009) Chronic Disease Prevention and Health Promotion. The power to prevent, The Call to Control: At a Glance 2009. Retrieved October 28, 2013, from http://www.cdc.gov/chronicdisease/resources/publications/aag/chronic.htm Centers for Disease Control and Prevention. (2013). Get the Lead Out: National Lead Poisoning Prevention Week 2013. Retrieved October 28, 2013, from http://blogs.cdc.gov/yourhealthyourenvironment/2013/10/23/get-the-lead-out-national-lead-poisoning-prevention-week-2013/ Donatelle, R. J. (2011). Health. The Basics, Green Edition. Retrieved from The University ofPhoenix eBook Collection database. How to boost your immune system. (2013). Retrieved October 29, 2013 from http://www.health.harvard.edu/flu resource-center/how-to-boost-your-immune-system.htm Smoking. (2013). Retrieved October 31, 2013 from http://www.lung.org/stop-smoking/about smoking/health-effects/smoking.html

Explain How Products Are Developed Essay

3.1.1 The product life cycle (PLC). The product life cycle is used for determining the lifespan of products and there are 4 sub stages of product: introduction, growth, maturity and decline. From 2007 until now, Honda Air Blade has become the most successful line of Honda’s motorbike as well as on market. Since it was born, Honda Air Blade has achieved sales of more than 2 million products. This year, from April to the end of September, Honda Air Blade reaches to 274,563 products. (Zing, 2014) This motorbike has brought more profits and impacted strongly on revenue of company. Honda has had the success with this product line. But in the modern world, to be able to compete with the competitors, Honda needs to improve quality, style of products and consider market prices as well as competitors to make a better product 3.1.2. Branding and brand leadership. a. Branding: A brand is much bigger than just the corporate logo. The brand attributes are formed from the efforts of corporation in the process of marketing communication activities and the character of business. Therefore, corporation needs to have an appropriate strategy to release a good PR campaign to make them more attractive than the competitors. Honda has slogan:† The power of dreams†, easily to remember and it has been very famous around the world. b. Brand leadership: The first appearance of Honda in Vietnam is in 1996, until now has been through 18 years and they have always been one of the forefront in their industry. (Honda, 2014) But now, Vietnam’s market has Yamaha, the biggest rival of Honda and the competition between both will continue for a long time in the future. Consequently, Honda has to use and combine an ingenious of design, advertising, marketing, and corporate culture. It will help create brand attributes in the minds of the people and that this will bring

Women in Ancient Greek Marriages

The Greeks thought that Cecrops—one of the early kings of Athens who wasnt entirely human—was responsible for civilizing mankind and establishing monogamous marriage. Men were still free to establish relationships with courtesans and prostitutes, but with the institution of matrimony, lines of heredity could be traced, and marriage established who was in charge of the woman. Marriage Partners Since citizenship was passed through to ones offspring, there were limits on whom a citizen might marry. With the enactment of Pericles citizenship laws, resident aliens—or metics—were suddenly taboo. As in the Oedipus story, mothers were taboo, as were full sisters, but uncles might marry nieces and brothers could mary their half-sisters primarily in order to keep property in the family. Types of Marriage There were two basic types of marriage that provided legitimate offspring. In one, the male legal guardian (kurios) who had charge of the woman arranged her marriage partner. This type of marriage is called enguesis betrothal. If a woman was an heiress without a kurios, she was called an epikleros and might be (re-)married by the marriage form known as epidikasia. Marital Obligations of the Greek Heiress It was unusual for a woman to own property, so the marriage of an epikleros was to the next closest available male in the family, who thereby gained control of the property. If the woman were not an heiress, the archon would find a close male relative to marry her and become her kurios. Women married in this way produced sons who were legal heirs to their fathers property. The dowry was an important provision for the woman since she would not inherit her husbands property. It was established at the enguesis. The dowry would have to provide for the woman in case of either death or divorce, but it would be managed by her kurios. The Month for Marriage One of the months of the Athenian calendar was called Gamelion for the Greek word for wedding. It was in this winter month that most Athenian weddings took place. The ceremony was a complicated ceremony involving sacrifice and other rituals, including registration of the wife in the phratry of the husband. Greek Womens Living Quarters The wife lived in the gynaikonitis womens quarters where she overlooked the management of the home, tended to the educational needs of the young children, and of any daughters until marriage, cared for the sick, and made clothing.