Measurement of the hydride donor abilities of [HM(diphosphine)2]+ complexes (M = Ni, Pt) by heterolytic activation of hydrogen.

[M(diphosphine)2]2+ complexes (where M = Ni and Pt) react with hydrogen in the presence of bases to form the corresponding hydrides, [HM(diphosphine)2]+. In seven cases, equilibria have been observed from which the hydride donor ability (DeltaGdegrees(H-)) of the hydrides can be calculated. For six of these complexes, the DeltaGdegrees(H-) values calculated using heterolytic activation of hydrogen are compared with those based on thermodynamic cycles using pK(a) measurements and electrochemical half-wave potentials. The agreement between these two methods is good (within 1 kcal/mol). The reactivity of the various [M(diphosphine)2]2+ complexes toward hydrogen parallels their measured hydride acceptor abilities.