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 language | English |
|---|---|
| Pages (from-to) | 365-373 |
| Number of pages | 9 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 290 |
| Issue number | 3 |
| DOIs | |
| State | Published - Aug 6 1985 |
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ASJC Scopus subject areas
- Biochemistry
- Chemical Engineering (miscellaneous)
- Inorganic Chemistry
- Organic Chemistry
- Physical and Theoretical Chemistry
- Materials Science (miscellaneous)
- Materials Chemistry
Cite this
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. / Nolan, Steven P.; Hoff, Carl.
In: Journal of Organometallic Chemistry, Vol. 290, No. 3, 06.08.1985, p. 365-373.Research output: Contribution to journal › Article
}
TY - JOUR
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
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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UR - http://www.scopus.com/inward/citedby.url?scp=0001240843&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(85)87299-5
DO - 10.1016/0022-328X(85)87299-5
M3 - Article
AN - SCOPUS:0001240843
VL - 290
SP - 365
EP - 373
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 3
ER -