Structural, spectroscopic, and electrochemical studies of the complexes [Ni2(mu-CNR)(CNR)2(mu-dppm)2](n+) (n = 0, 1, 2): unusual examples of nickel(0)-nickel(I) and nickel(0)-nickel(II) mixed valency.

Abstract

Reaction of Ni(COD)(2) (COD = cyclooctadiene) with dppm (dppm = bis(diphenylphosphino) methane) followed by addition of alkyl or aryl isocyanides yields the class of nickel(0) dimers Ni(2)(mu-CNR)(CNR)(2)(mu-dppm)(2) (R = CH(3) (1), n-C(4)H(9) (2), CH(2)C(6)H(5) (3), i-C(3)H(7) (4), C(6)H(11) (5), t-C(4)H(9) (6), p-IC(6)H(4) (7), 2,6-(CH(3))(2)C(6)H(3) (8)). The cyclic voltammograms of the dimers exhibit two sequential single electron oxidations to the +1 and +2 forms. Specular reflectance infrared spectroelectrochemical (IRSEC) measurements demonstrate reversible interconversions between the neutral Ni(0) dimers and their +1 and +2 forms. Bulk samples of the +2 forms are prepared by chemical oxidation using [FeCp(2)][PF(6)], while the +1 forms are prepared by the comproportionation of neutral and +2 forms. The neutral complexes 6 and 8 were characterized by X-ray diffraction as symmetric, locally tetrahedral binuclear Ni(0) complexes. The +2 forms of these complexes, 6(2+) and 8(2+), have asymmetric structures with one locally square planar and one locally tetrahedral metal center, evidence for a Ni(II)-Ni(0) mixed valence state. The X-ray structural characterization of 6(+) is symmetrical and qualitatively similar to that of the neutral complex 6. The +1 forms all exhibit intense near IR electronic absorptions that are assigned as intervalence charge transfer (IVCT) bands. On the basis of structural, spectroscopic, and electrochemical data, the +1 forms of the complexes, 1(+)-8(+), are assigned as Robin-Day class III, fully delocalized Ni(+0.5)-Ni(+0.5) mixed valence complexes.