The thermodynamic driving force for CH activation at iridium

Page O. Stoutland, Robert G. Bergman, Steven P. Nolan, Carl Hoff

Research output: Contribution to journalArticle

73 Citations (Scopus)

Abstract

This paper discusses the relationship between the intermolecular oxidative addition reaction of carbon-hydrogen bonds in organic molecules to transition metal centres, and the dissociation energies of the CH, MH and MR bonds that undergo changes during this process. Earlier studies of transition metal MH and MR bond energies are reviewed, followed by a summary of relative and absolute bond energies measured more recently for the (η5-C5Me5)(PMe3)Ir(X)(Y) system. The MH and MR energies are unusually large in this system compared with most others that are presently known; an important exception are those in the thorium series, where intermolecular CH activation is also observed. The IrC and IrH bond energy values are utilized in discussing the propensity of iridium for intermolecular CH insertion, and in predicting thermochemistries for its RH insertion and M(H)(R) reductive elimination reactions. Finally, the physical basis for the strong metal-carbon and -hydrogen bonds in the iridium system is discussed.

Original languageEnglish
Pages (from-to)1429-1440
Number of pages12
JournalPolyhedron
Volume7
Issue number16-17
DOIs
StatePublished - Jan 1 1988

Fingerprint

Iridium
iridium
Thermodynamics
Transition metals
Hydrogen bonds
Carbon
Metals
Chemical activation
activation
methylidyne
Thorium
Thermochemistry
thermodynamics
Addition reactions
Hydrogen
insertion
Molecules
transition metals
energy
hydrogen bonds

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

The thermodynamic driving force for CH activation at iridium. / Stoutland, Page O.; Bergman, Robert G.; Nolan, Steven P.; Hoff, Carl.

In: Polyhedron, Vol. 7, No. 16-17, 01.01.1988, p. 1429-1440.

Research output: Contribution to journalArticle

Stoutland, PO, Bergman, RG, Nolan, SP & Hoff, C 1988, 'The thermodynamic driving force for CH activation at iridium', Polyhedron, vol. 7, no. 16-17, pp. 1429-1440. https://doi.org/10.1016/S0277-5387(00)81772-6
Stoutland, Page O. ; Bergman, Robert G. ; Nolan, Steven P. ; Hoff, Carl. / The thermodynamic driving force for CH activation at iridium. In: Polyhedron. 1988 ; Vol. 7, No. 16-17. pp. 1429-1440.
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