The heats of reaction of phosphines and phosphites with toluene-molybdenum tricarbonyl. Importance of both steric and electronic factors in determining the MoPR3 bond strength

Steven P. Nolan, Carl D. Hoff

Research output: Contribution to journalArticle

52 Scopus citations

Abstract

The heats of reaction of tolueneMo(CO)3 with a series of phosphines and phosphites have been measured by solution calorimetry. The order of stability toward formation of fac-(PR3)3Mo(CO)3 in THF solution is: P(OCH3)3s > PMe3 > PnBu3 > PMe2Ph > PEt3 > triphos > P(OPh)3 > PMePh2 > PPh3 > PCl3 and spans a range of 25 kcal/mol reflecting individual bond strength differences up to 8 kcal/mol. The bulky phosphines PCy3 and PtBu3 react with tolueneMo(CO)3 in THF, but 30-40 kcal/mol less heat is evolved in these reactions than with the other phosphines and phosphites. The coordinately unsaturated five-coordinate complexes (PR3)2Mo(CO)3 are proposed as the reaction products. The importance of both steric and electronic factors in the MoP bond is discussed.

Original languageEnglish (US)
Pages (from-to)365-373
Number of pages9
JournalJournal of Organometallic Chemistry
Volume290
Issue number3
DOIs
StatePublished - Aug 6 1985

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Fingerprint Dive into the research topics of 'The heats of reaction of phosphines and phosphites with toluene-molybdenum tricarbonyl. Importance of both steric and electronic factors in determining the MoPR<sub>3</sub> bond strength'. Together they form a unique fingerprint.

  • Cite this