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

Calvin J. Curtis, Alex Miedaner, William W. Ellis, Daniel L DuBois

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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.

Original languageEnglish
Pages (from-to)1918-1925
Number of pages8
JournalJournal of the American Chemical Society
Volume124
Issue number9
DOIs
Publication statusPublished - Mar 6 2002

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Hydrides
Hydrogen
Chemical activation
Thermodynamics

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  • Chemistry(all)

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Measurement of the hydride donor abilities of [HM(diphosphine)2]+ complexes (M = Ni, Pt) by heterolytic activation of hydrogen. / Curtis, Calvin J.; Miedaner, Alex; Ellis, William W.; DuBois, Daniel L.

In: Journal of the American Chemical Society, Vol. 124, No. 9, 06.03.2002, p. 1918-1925.

Research output: Contribution to journalArticle

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