Empirical force-field calculations on a model system for trimesityl derivatives of group IIIa, IVa, and Va elements. Investigation of stereoisomerization pathways

Mandes R. Kates, Joseph D. Andose, Paolo Finocchiaro, John Devens Gust, Kurt Mislow

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Abstract

Stereoisomerization in the class of compounds (Mes)3Z (Mes = mesityl; Z = B, CH, N, etc.) has been investigated using the technique of empirical force-field calculations. The study was made feasible by employing a simplified model based on trimesitylmethane in which the only distinction among molecules in this class was the difference in the preferred length of the Z-Mes bond. Calculated energies for the idealized transition states point to the two-ring flip mechanism as the pathway of lowest energy over a wide range of structures. Calculated energies for this mechanism follow a trend which parallels experimental values. Activation energies are predicted for (Mes)3N, (Mes)3SnH, and (Mes)3Bi of 25-27, 5-7, and 3-5 kcal/ mol, respectively. Results for the higher energy mechanisms are discussed in terms of structural changes accompanying the change in bond length to the central atom. The three-ring flip is found to be consistently higher in energy than the two-ring flip in the region of interest.

Original languageEnglish
Pages (from-to)1772-1778
Number of pages7
JournalJournal of the American Chemical Society
Volume97
Issue number7
Publication statusPublished - 1975

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Bond length
Activation energy
Derivatives
Atoms
Molecules

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Empirical force-field calculations on a model system for trimesityl derivatives of group IIIa, IVa, and Va elements. Investigation of stereoisomerization pathways. / Kates, Mandes R.; Andose, Joseph D.; Finocchiaro, Paolo; Gust, John Devens; Mislow, Kurt.

In: Journal of the American Chemical Society, Vol. 97, No. 7, 1975, p. 1772-1778.

Research output: Contribution to journalArticle

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N2 - Stereoisomerization in the class of compounds (Mes)3Z (Mes = mesityl; Z = B, CH, N, etc.) has been investigated using the technique of empirical force-field calculations. The study was made feasible by employing a simplified model based on trimesitylmethane in which the only distinction among molecules in this class was the difference in the preferred length of the Z-Mes bond. Calculated energies for the idealized transition states point to the two-ring flip mechanism as the pathway of lowest energy over a wide range of structures. Calculated energies for this mechanism follow a trend which parallels experimental values. Activation energies are predicted for (Mes)3N, (Mes)3SnH, and (Mes)3Bi of 25-27, 5-7, and 3-5 kcal/ mol, respectively. Results for the higher energy mechanisms are discussed in terms of structural changes accompanying the change in bond length to the central atom. The three-ring flip is found to be consistently higher in energy than the two-ring flip in the region of interest.

AB - Stereoisomerization in the class of compounds (Mes)3Z (Mes = mesityl; Z = B, CH, N, etc.) has been investigated using the technique of empirical force-field calculations. The study was made feasible by employing a simplified model based on trimesitylmethane in which the only distinction among molecules in this class was the difference in the preferred length of the Z-Mes bond. Calculated energies for the idealized transition states point to the two-ring flip mechanism as the pathway of lowest energy over a wide range of structures. Calculated energies for this mechanism follow a trend which parallels experimental values. Activation energies are predicted for (Mes)3N, (Mes)3SnH, and (Mes)3Bi of 25-27, 5-7, and 3-5 kcal/ mol, respectively. Results for the higher energy mechanisms are discussed in terms of structural changes accompanying the change in bond length to the central atom. The three-ring flip is found to be consistently higher in energy than the two-ring flip in the region of interest.

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