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 Hoff

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

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Phosphines
Phosphites
Molybdenum
Toluene
Carbon Monoxide
phosphines
molybdenum
toluene
Hot Temperature
heat
Calorimetry
Reaction products
electronics
reaction products
heat measurement

ASJC Scopus subject areas

  • Biochemistry
  • Chemical Engineering (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Science (miscellaneous)
  • Materials Chemistry

Cite this

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title = "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",
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.",
author = "Nolan, {Steven P.} and Carl Hoff",
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T1 - 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

AU - Nolan, Steven P.

AU - Hoff, Carl

PY - 1985/8/6

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N2 - 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.

AB - 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.

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