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

Research output: Contribution to journalArticle

53 Citations (Scopus)

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

Fingerprint

Proton transfer
Hydrides
Transition metals
Hydrogen
Hydrogen bonds
Metals
Atoms
Ligands
Nucleophiles
Exothermic reactions
Alkenes
Organometallics
Protons
Carbon
Thermodynamics

Keywords

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

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{5a3ed4124bd64c30ab122fcf8ddcd2b1,
title = "Metal-Hydrogen Bond Cleavage Reactions of Transition Metal Hydrides: Hydrogen Atom, Hydride, and Proton Transfer Reactions",
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.",
keywords = "fer olefin hydrogenation, hydride trans-, hydrogen atom transfer, metal hydrides, proton transfer",
author = "Bullock, {R Morris}",
year = "1991",
doi = "10.1080/02603599108018617",
language = "English",
volume = "12",
pages = "1--33",
journal = "Comments on Inorganic Chemistry",
issn = "0260-3594",
publisher = "Taylor and Francis Ltd.",
number = "1",

}

TY - JOUR

T1 - Metal-Hydrogen Bond Cleavage Reactions of Transition Metal Hydrides

T2 - Hydrogen Atom, Hydride, and Proton Transfer Reactions

AU - Bullock, R Morris

PY - 1991

Y1 - 1991

N2 - 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.

AB - 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.

KW - fer olefin hydrogenation

KW - hydride trans-

KW - hydrogen atom transfer

KW - metal hydrides

KW - proton transfer

UR - http://www.scopus.com/inward/record.url?scp=84917924500&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84917924500&partnerID=8YFLogxK

U2 - 10.1080/02603599108018617

DO - 10.1080/02603599108018617

M3 - Article

AN - SCOPUS:84917924500

VL - 12

SP - 1

EP - 33

JO - Comments on Inorganic Chemistry

JF - Comments on Inorganic Chemistry

SN - 0260-3594

IS - 1

ER -