title: Measurement of the hydride donor abilities of [HM(diphosphine)2]+ complexes (M = Ni, Pt) by heterolytic activation of hydrogen.
abstract: [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.
authors.affiliation: Contribution from the National Renewable Energy Laboratory, 1617 Cole Boulevard, Golden, Colorado 80401, USA.
authors.forename: Calvin J
authors.initials: CJ
authors.lastname: Curtis
authors.forename: Alex
authors.initials: A
authors.lastname: Miedaner
authors.forename: William W
authors.initials: WW
authors.lastname: Ellis
authors.forename: Daniel L
authors.initials: DL
authors.lastname: DuBois