Metal-Hydrogen Bond Cleavage Reactions of Transition Metal Hydrides: Hydrogen Atom, Hydride, and Proton Transfer Reactions

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Abstract

Cleavage of the M-H bond of transition metal hydrides can result in delivery of a hydride (H~), hydrogen atom (H or proton (H+) to an organic or organometallic substrate. Hydrogen atom transfer from a metal hydride to an olefin is an endothermic reaction; the rate at which different metal hydrides carry out this reaction is mainly dependent on the bond dissociation energy of ttie M-H bond. Hydrogen atom transfer from a metal hydride to a carbon-centered radical is an exothermic reaction in which the rate is largely determined by steric demands of the ligands of the metal hydride, with thermodynamics playing a less important role. Some neutral metal hydrides can function as hydride donors to carbocations. Anionic metal hydrides also exhibit hydridic reactivity, but in some cases the actual M-H bond cleavage step involves hydrogen atom transfer as a part of a radical chain reaction. Neutral metal hydrides can function as nucleophiles and as weakly ‘coordinating ligands to coordinatively unsaturated metals.

Original languageEnglish
Pages (from-to)1-33
Number of pages33
JournalComments on Inorganic Chemistry
Volume12
Issue number1
DOIs
Publication statusPublished - 1991

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Keywords

  • fer olefin hydrogenation
  • hydride trans-
  • hydrogen atom transfer
  • metal hydrides
  • proton transfer

ASJC Scopus subject areas

  • Inorganic Chemistry

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