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

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

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

101 Citations (Scopus)

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 pK_a 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.

Original language	English
Pages (from-to)	1832-1839
Number of pages	8
Journal	Organometallics
Volume	20
Issue number	9
Publication status	Published - Apr 30 2001

ASJC Scopus subject areas

Inorganic Chemistry
Organic Chemistry

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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 journal › Article › peer-review

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

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.",

author = "Berning, {Douglas E.} and Alex Miedaner and Curtis, {Calvin J.} and Noll, {Bruce C.} and {Rakowski DuBois}, {Mary C.} and DuBois, {Daniel L}",

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T1 - Free-energy relationships between the proton and hydride donor abilities of [HNi(diphosphine)2]+ complexes and the half-wave potentials of their conjugate bases

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

Y1 - 2001/4/30

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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