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

Research output: Contribution to journalArticle

69 Citations (Scopus)

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

ASJC Scopus subject areas

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes'. Together they form a unique fingerprint.

  • Cite this