Thermodynamic hydride donor abilities of [HW(CO)4L]- complexes (L = PPH3, P(OMe)3, CO) and their reactions with [C5Me5Re(PMe3)(NO)(CO)]+

William W. Ellis, Rebecca Ciancanelli, Susie M. Miller, James W. Raebiger, M. Rakowski DuBois, Daniel L DuBois

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Abstract

Abstract: The thermodynamic hydride donor abilities of [HW(CO) 5]- (40 kcal/mol), [HW(CO)4P(OMe 3)]- (37 kcal/mol), and [HW(CO)4(PPh 3)]- (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(PPh 3)]- all react rapidly with [Cp*Re(PMe 3)(NO)(CO)]+ to form dinuclear intermediates with bridging formyl ligands. These intermediates slowly form [Cp*Re(PMe 3)(NO)(CHO)] and [W(CO)4(L)(CH3- CN)]. 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.

Original languageEnglish
Pages (from-to)12230-12236
Number of pages7
JournalJournal of the American Chemical Society
Volume125
Issue number40
DOIs
Publication statusPublished - Oct 8 2003

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Carbon Monoxide
Thermodynamics
Hydrides
Ligands
Acetonitrile

ASJC Scopus subject areas

  • Chemistry(all)

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Thermodynamic hydride donor abilities of [HW(CO)4L]- complexes (L = PPH3, P(OMe)3, CO) and their reactions with [C5Me5Re(PMe3)(NO)(CO)]+ . / Ellis, William W.; Ciancanelli, Rebecca; Miller, Susie M.; Raebiger, James W.; DuBois, M. Rakowski; DuBois, Daniel L.

In: Journal of the American Chemical Society, Vol. 125, No. 40, 08.10.2003, p. 12230-12236.

Research output: Contribution to journalArticle

Ellis, William W. ; Ciancanelli, Rebecca ; Miller, Susie M. ; Raebiger, James W. ; DuBois, M. Rakowski ; DuBois, Daniel L. / Thermodynamic hydride donor abilities of [HW(CO)4L]- complexes (L = PPH3, P(OMe)3, CO) and their reactions with [C5Me5Re(PMe3)(NO)(CO)]+ . In: Journal of the American Chemical Society. 2003 ; Vol. 125, No. 40. pp. 12230-12236.
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abstract = "Abstract: The thermodynamic hydride donor abilities of [HW(CO) 5]- (40 kcal/mol), [HW(CO)4P(OMe 3)]- (37 kcal/mol), and [HW(CO)4(PPh 3)]- (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(PPh 3)]- all react rapidly with [Cp*Re(PMe 3)(NO)(CO)]+ to form dinuclear intermediates with bridging formyl ligands. These intermediates slowly form [Cp*Re(PMe 3)(NO)(CHO)] and [W(CO)4(L)(CH3- CN)]. 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.",
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AU - Ellis, William W.

AU - Ciancanelli, Rebecca

AU - Miller, Susie M.

AU - Raebiger, James W.

AU - DuBois, M. Rakowski

AU - DuBois, Daniel L

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N2 - Abstract: The thermodynamic hydride donor abilities of [HW(CO) 5]- (40 kcal/mol), [HW(CO)4P(OMe 3)]- (37 kcal/mol), and [HW(CO)4(PPh 3)]- (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(PPh 3)]- all react rapidly with [Cp*Re(PMe 3)(NO)(CO)]+ to form dinuclear intermediates with bridging formyl ligands. These intermediates slowly form [Cp*Re(PMe 3)(NO)(CHO)] and [W(CO)4(L)(CH3- CN)]. 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.

AB - Abstract: The thermodynamic hydride donor abilities of [HW(CO) 5]- (40 kcal/mol), [HW(CO)4P(OMe 3)]- (37 kcal/mol), and [HW(CO)4(PPh 3)]- (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(PPh 3)]- all react rapidly with [Cp*Re(PMe 3)(NO)(CO)]+ to form dinuclear intermediates with bridging formyl ligands. These intermediates slowly form [Cp*Re(PMe 3)(NO)(CHO)] and [W(CO)4(L)(CH3- CN)]. 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.

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