Measurement of the Hydride Donor Abilities of [HM(diphosphine)2]+ Complexes (M = Ni, Pt) by Heterolytic Activation of Hydrogen
- 8 February 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (9) , 1918-1925
- https://doi.org/10.1021/ja0116829
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 (ΔG°H−) of the hydrides can be calculated. For six of these complexes, the ΔG°H− values calculated using heterolytic activation of hydrogen are compared with those based on thermodynamic cycles using pKa 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.Keywords
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