| Sumario: | The mixed-ligand complex [Ni(dppp)(PN)](BF), 3, (where PN is 1,5-dibenzyl-3,7- diphenyl-1,5-diaza-3,7-diphosphacyclooctane and dppp is 1,3-bis(diphenylphosphino)propane) has been synthesized. Treatment of this complex with H and triethylamine results in the formation of the Ni complex, Ni(dppp)(PN), 4, whose structure has been determined by a single-crystal X-ray diffraction study. Heterolytic cleavage of H by 3 at room temperature forms [HNi(dppp)(PN(μ-H)N](BF), 5a, in which one proton interacts with two nitrogen atoms of the cyclic diphosphine ligand and a hydride ligand is bound to nickel. Two intermediates are observed for this reaction using low-temperature NMR spectroscopy. One species is a dihydride, [(H)Ni(dppp)(PN)](BF), 5b, and the other is [Ni(dppp)(PNH)](BF)2, 5c, in which both protons are bound to the N atoms in an endo geometry with respect to nickel. These two species interconvert via a rapid and reversible intramolecular proton exchange between nickel and the nitrogen atoms of the diphosphine ligand. Complex 3 is a catalyst for the electrochemical oxidation of H in the presence of base, and new insights into the mechanism derived from low-temperature NMR and thermodynamic studies are presented. A comparison of the rate and thermodynamics of H addition for this complex to related catalysts studied previously indicates that for Ni complexes containing two diphosphine ligands, the activation of H is favored by the presence of two positioned pendant bases.
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