Thermodynamic studies of [H2Rh(diphosphine)2] + and [HRh(diphosphine)2(CH3CN)]2+ complexes in acetonitrile

Aaron D. Wilson, Alexander J M Miller, Daniel L DuBois, Jay A. Labinger, John E. Bercaw

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

Thermodynamic studies of a series of [H2Rh(PP)2] + and [HRh(PP)2(CH3CN)]2+ complexes have been carried out in acetonitrile. Seven different diphosphine (PP) ligands were selected to allow variation of the electronic properties of the ligand substituents, the cone angles, and the natural bite angles (NBAs). Oxidative addition of H2 to [Rh(PP)2]+ complexes is favored by diphosphine ligands with large NBAs, small cone angles, and electron donating substituents, with the NBA being the dominant factor. Large pK a values for [HRh(PP)2(CH3CN)]2+ complexes are favored by small ligand cone angles, small NBAs, and electron donating substituents with the cone angles playing a major role. The hydride donor abilities of [H2Rh(PP)2]+ complexes increase as the NBAs decrease, the cone angles decrease, and the electron donor abilities of the substituents increase. These results indicate that if solvent coordination is involved in hydride transfer or proton transfer reactions, the observed trends can be understood in terms of a combination of two different steric effects, NBAs and cone angles, and electron-donor effects of the ligand substituents.

Original languageEnglish
Pages (from-to)3918-3926
Number of pages9
JournalInorganic Chemistry
Volume49
Issue number8
DOIs
Publication statusPublished - Apr 19 2010

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acetonitrile
Cones
Thermodynamics
thermodynamics
Ligands
cones
Electrons
Hydrides
ligands
Proton transfer
Electronic properties
hydrides
electrons
trends
protons

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Thermodynamic studies of [H2Rh(diphosphine)2] + and [HRh(diphosphine)2(CH3CN)]2+ complexes in acetonitrile. / Wilson, Aaron D.; Miller, Alexander J M; DuBois, Daniel L; Labinger, Jay A.; Bercaw, John E.

In: Inorganic Chemistry, Vol. 49, No. 8, 19.04.2010, p. 3918-3926.

Research output: Contribution to journalArticle

Wilson, Aaron D. ; Miller, Alexander J M ; DuBois, Daniel L ; Labinger, Jay A. ; Bercaw, John E. / Thermodynamic studies of [H2Rh(diphosphine)2] + and [HRh(diphosphine)2(CH3CN)]2+ complexes in acetonitrile. In: Inorganic Chemistry. 2010 ; Vol. 49, No. 8. pp. 3918-3926.
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