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

Research output: Contribution to journalArticle

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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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Hydrides
Free energy
hydrides
Protons
free energy
protons
Nickel
Molecular structure
Single crystals
X ray diffraction
cleavage
molecular structure
nickel
single crystals
diffraction
x rays

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Free-energy relationships between the proton and hydride donor abilities of [HNi(diphosphine)2]+ complexes and the half-wave potentials of their conjugate bases. / Berning, Douglas E.; Miedaner, Alex; Curtis, Calvin J.; Noll, Bruce C.; Rakowski DuBois, Mary C.; DuBois, Daniel L.

In: Organometallics, Vol. 20, No. 9, 30.04.2001, p. 1832-1839.

Research output: Contribution to journalArticle

Berning, Douglas E. ; Miedaner, Alex ; Curtis, Calvin J. ; Noll, Bruce C. ; Rakowski DuBois, Mary C. ; DuBois, Daniel L. / Free-energy relationships between the proton and hydride donor abilities of [HNi(diphosphine)2]+ complexes and the half-wave potentials of their conjugate bases. In: Organometallics. 2001 ; Vol. 20, No. 9. pp. 1832-1839.
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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°H·, 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.",
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AU - Berning, Douglas E.

AU - Miedaner, Alex

AU - Curtis, Calvin J.

AU - Noll, Bruce C.

AU - Rakowski DuBois, Mary C.

AU - DuBois, Daniel L

PY - 2001/4/30

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N2 - 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°H·, 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.

AB - 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°H·, 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.

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