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2007
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March
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In the Laboratory
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Experiments in Thermodynamics and Kinetics of Phosphine Substitution in (p-Cymene)RuCl2(PR3)
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Oleg V. Ozerov and Claudia M. Fafard
Department of Chemistry, Brandeis University, Waltham, MA 02454
Norris W. Hoffman
Department of Chemistry, University of South Alabama, Mobile, AL 36688
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March 2007
Vol. 84 No. 3
p. 489
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| Abstract |
| This manuscript describes a set of three experiments that investigates the thermodynamic and kinetic aspects of phosphine substitution at a Ru center. In the first experiment, the students synthesize a Ru organometallic complex containing a phosphine ligand. In the second, equilibria for phosphine substitution involving several different phosphines are studied. The equilibrium constants are converted into free energies of reactions which are compared with data from literature thermochemical studies. In the third experiment, the kinetics of the substitution of tris(p-fluorophenyl)phosphine is studied using variable-temperature (25–60 °C range) 19F NMR. The kinetic studies confirm that this reaction follows a simple first-order rate law. With some approximations, combining the data obtained here and the literature thermochemical data allow estimation of the strength of a bridging Ru–Cl bond in the starting material used in this laboratory set. The materials used in these experiments are relatively inexpensive and air-stable.
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| Supplement |
Descriptions of the experiments, graphs of the kinetic data, and laboratory handouts are available.
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| More Information |
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Citation |
Ozerov, Oleg V.; Fafard, Claudia M.; Hoffman, Norris W. J. Chem. Educ. 2007 84 489.
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Keywords |
Coordination Compounds; Hands-On Learning / Manipulatives; Inorganic Chemistry; Kinetics; Laboratory Instruction; NMR Spectroscopy; Organometallics; Rate Law; Ruthenium; Thermodynamics; Upper-Division Undergraduate
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History |
Created:
Last Updated: |
2/1/2007
2/22/2007
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 Caution! | | Experiments, laboratory exercises, lecture demonstrations, and other descriptions of the use of chemicals, apparatus, instruments, computers, and computer interfaces are presented in the Journal of Chemical Education as illustrative of new or improved ideas or concepts in chemistry instruction and are directed at qualified teachers. Although every effort is made to assure and encourage safe practices and safe use of chemicals, the Journal of Chemical Education cannot assume responsibility for uses made of its published materials. Many chemicals are hazardous. Precautions for the safe use of hazardous chemicals and directions for their proper disposal are described in the Material Safety Data Sheets and on the labels. We strongly urge all those planning to use materials from our pages to make choices and to develop procedures for laboratory and classroom safety in accordance with local needs and situations. |
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489
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