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

doi:10.1016/0022-328X(85)87299-5

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

Chemistry

Research output: Contribution to journal › Article › peer-review

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 P^tBu₃ 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 language	English (US)
Pages (from-to)	365-373
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	290
Issue number	3
DOIs	https://doi.org/10.1016/0022-328X(85)87299-5
State	Published - Aug 6 1985

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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@article{e0b84f4cabe045c59c3578186f63d06e,

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 Hoff, {Carl D.}",

note = "Funding Information: Support of this work by the National ScienceF oundation (Grant No. 8314497i)s gratefullya cknowledged.",

year = "1985",

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doi = "10.1016/0022-328X(85)87299-5",

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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 D.

N1 - Funding Information: Support of this work by the National ScienceF oundation (Grant No. 8314497i)s gratefullya cknowledged.

PY - 1985/8/6

Y1 - 1985/8/6

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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