Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes

William W. Ellis, Alex Miedaner, Calvin J. Curtis, Dorothy H. Gibson, Daniel L DuBois

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Abstract

The hydride complex [Pt(dmpe)2H]+ (dmpe = 1,2-bis(dimethylphosphino)ethane) reversibly transfers H- to the rhenium carbonyl complex [CpRe(PMe3)(NO)(CO)]+, giving the formyl CpRe(PMe3)(NO) (CHO). From the equilibrium constant for the hydride transfer (16.2), the ΔG° for the reaction was determined (-1.6 kcal/mol), as was the hydride-donating ability of the formyl (44.1 kcal/mol). The hydride-donating donating ability, ΔG°H-, is defined as the energy required to release the hydride ion into solution by the formyl complex [i.e. M(CHO) → M(CO)+ + H-]. Subsequently, the hydride-donating ability of a series of formyl complexes was determined, ranging from 44 to 55 kcal/mol. With use of this information, two rhenium carbonyl complexes, [CpRe(NO)(CO)2]+and [Cp*Re(NO)(CO)2]+, were hydrogenated to formyls, employing [Pt(dmpp)2]2+ and Proton-Sponge. Finally, the E1/2(I/0) values for five rhenium carbonyl complexes were measured by cyclic voltammetry. Combined with the known ΔG°H- values for the complexes, the hydrogen atom donating abilities could be determined. These values were all found to be approximately 50 kcal/mol.

Original languageEnglish
Pages (from-to)1926-1932
Number of pages7
JournalJournal of the American Chemical Society
Volume124
Issue number9
DOIs
Publication statusPublished - Mar 6 2002

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Rhenium
Coordination Complexes
Metal complexes
Hydrides
Free energy
Transition metals
Ethane
Porifera
Protons
Hydrogen
Ions
Equilibrium constants
Cyclic voltammetry
Atoms

ASJC Scopus subject areas

  • Chemistry(all)

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Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes. / Ellis, William W.; Miedaner, Alex; Curtis, Calvin J.; Gibson, Dorothy H.; DuBois, Daniel L.

In: Journal of the American Chemical Society, Vol. 124, No. 9, 06.03.2002, p. 1926-1932.

Research output: Contribution to journalArticle

Ellis, William W. ; Miedaner, Alex ; Curtis, Calvin J. ; Gibson, Dorothy H. ; DuBois, Daniel L. / Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes. In: Journal of the American Chemical Society. 2002 ; Vol. 124, No. 9. pp. 1926-1932.
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