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

doi:10.1021/ja0116829

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

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

184 Citations (Scopus)

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 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.

Original language	English
Pages (from-to)	1918-1925
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	124
Issue number	9
DOIs	https://doi.org/10.1021/ja0116829
Publication status	Published - Mar 6 2002

ASJC Scopus subject areas

Chemistry(all)

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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.",

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AU - Miedaner, Alex

AU - Ellis, William W.

AU - DuBois, Daniel L

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AB - [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.

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