Free-Energy Relationships between the Proton and Hydride Donor Abilities of [HNi(diphosphine)2]+ Complexes and the Half-Wave Potentials of Their Conjugate Bases
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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/0) 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(Et2PCH2CH2PPh2)2 and Ni(Ph2PCHCHPPh2)2 were determined by single-crystal X-ray diffraction studies.
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