Thermodynamic Studies of HRh(depx) 2 and [(H) 2Rh(depx) 2](CF 3so 3): Relationships between Five-Coordinate Monohydrides and Six-Coordinate Dihydrides

James W. Raebiger, Daniel L. DuBois

Research output: Contribution to journalArticle

45 Citations (Scopus)

Abstract

Four new rhodium complexes, [Rh(depx) 2](CF 3SO 3), [(H) 2Rh(depx) 2](CF 3SO 3), [HRh(depx) 2(CH 3CN)](CF 3SO 3) 2, and HRh(depx) 2 (where depx = α,α′-bis(diethylphosphino)xylene), have been synthesized and characterized. The pK a values of [(H) 2Rh(depx) 2] + (30.6 ± 0.3) and [HRh(depx) 2(CH 3CN)] 2+ (11.5 ± 0.4) in acetonitrile were determined by equilibrium reactions with appropriate bases. The hydride donor ability of [(H) 2Rh(depx) 2] + (71.6 ± 1.0 kcal/mol) was determined by the heterolytic cleavage of hydrogen by [HRh(depx) 2(CH 3CN)] 2+ to form [(H) 2Rh(depx) 2] + in the presence of thioacetamide or benzamide. These equilibrium measurements, the half-wave potentials for the Rh(+l/0) and Kh(0/-l) couples of [Rh(depx) 2] +, and the reversible one-electron oxidation of HRh(depx) 2 (all measured at 22 ± 1.5 °C) were used to establish nine heterolytic and homolytic bond-dissociation free energies in acetonitrile. From these relationships, and those established previously for analogous cobalt and platinum complexes, we conclude that the homolytic bond-dissociation free energies of six-coordinate dihydride species are approximately 2 kcal/mol less than those of the corresponding five-coordinate monohydride species derived by deprotonation. Similarly, the pK a values of six-coordinate dihydride complexes are approximately 2 units lower than the corresponding five-coordinate species formally derived by homolytic bond cleavage.

Original languageEnglish
Pages (from-to)110-118
Number of pages9
JournalOrganometallics
Volume24
Issue number1
DOIs
Publication statusPublished - Jan 3 2005

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Thermodynamic Studies of HRh(depx) <sub>2</sub> and [(H) <sub>2</sub>Rh(depx) <sub>2</sub>](CF <sub>3</sub>so <sub>3</sub>): Relationships between Five-Coordinate Monohydrides and Six-Coordinate Dihydrides'. Together they form a unique fingerprint.

  • Cite this