Free-energy relationships between the proton and hydride donor abilities of [HNi(diphosphine)2]+ complexes and the half-wave potentials of their conjugate bases

Douglas E. Berning, Alex Miedaner, Calvin J. Curtis, Bruce C. Noll, Mary C. Rakowski DuBois, Daniel L DuBois

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Abstract

A linear free-energy relationship exists between the half-wave potentials of the (II/I) couples of Ni(diphosphine)2 complexes and the hydride donor ability (ΔG°H -) of the corresponding [HNi(diphosphine)2]+ complexes. A similar correlation is observed between the half-wave potentials of the (I/O) couples of Ni(diphosphine)2 complexes and the pKa values (or ΔG°H +) of the corresponding [HNi(diphosphine)2]+ complexes. As a result, it is possible to use the potentials of these two couples to predict the free energies of all three Ni-H bond cleavage reactions, ΔG°H+, ΔG°, and ΔG°H-, for this class of nickel complexes. The molecular structures of Ni(Et2PCH2CH2 PPh2)2 and Ni(Ph2PCHCHPPh2)2 were determined by single-crystal X-ray diffraction studies.

Original languageEnglish
Pages (from-to)1832-1839
Number of pages8
JournalOrganometallics
Volume20
Issue number9
Publication statusPublished - Apr 30 2001

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ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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