Thermodynamic Hydride Donor Abilities of [HW(CO)4L]-Complexes (L = PPh3, P(OMe)3, CO) and Their Reactions with [C5Me5Re(PMe3)(NO)(CO)]+
- 13 September 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (40), 12230-12236
- https://doi.org/10.1021/ja036524r
Abstract
The thermodynamic hydride donor abilities of [HW(CO)5]- (40 kcal/mol), [HW(CO)4P(OMe3)]- (37 kcal/mol), and [HW(CO)4(PPh3)]- (36 kcal/mol) have been measured in acetonitrile by either equilibrium or calorimetric methods. The hydride donor abilities of these complexes are compared with other complexes for which similar thermodynamic measurements have been made. [HW(CO)5]-, [HW(CO)4P(OMe3)]-, and [HW(CO)4(PPh3)]- all react rapidly with [Cp*Re(PMe3)(NO)(CO)]+ to form dinuclear intermediates with bridging formyl ligands. These intermediates slowly form [Cp*Re(PMe3)(NO)(CHO)] and [W(CO)4(L)(CH3CN)]. The structure of cis-[HW(CO)4(PPh3)]- has been determined and has the expected octahedral structure. The hydride ligand bends away from the CO ligand trans to PPh3 and toward PPh3.Keywords
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