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, Devens Gust, Kurt Mislow

Research output: Contribution to journalArticle

45 Scopus citations

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 (US)
Pages (from-to)1772-1778
Number of pages7
JournalJournal of the American Chemical Society
Volume97
Issue number7
DOIs
StatePublished - Apr 1 1975

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Empirical Force-Field Calculations on a Model System for Trimesityl Derivatives of Group IIIa, IVa, and Va Elements. Investigation of Stereoisomerization Pathways'. Together they form a unique fingerprint.

  • Cite this