Trends in Homolytic Bond Dissociation Energies of Five- and Six-Coordinate Hydrides of Group 9 Transition Metals

Co, Rh, Ir

Vassiliki Alexandra Glezakou, Roger Rousseau, Stephen T. Elbert, James A. Franz

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The homolytic bond dissociation energies of a series of five- and six-coordinate mono- and dihydride complexes of the type HM(diphosphine)2 and [H2M(diphosphine)2]+ (where M = Co, Rh, and Ir) are calculated and compared with experimental values. This work probes the relationship between the homolytic bond dissociation energies (HMBDEs) of these complexes in these two different coordination environments and formal oxidation states. The results of these calculations and previous experimental observations suggest that for M = Rh the HMBDE of the five-coordinate HM(diphosphine)2 species are 0-2 kcal/mol larger than the HMBDE of the corresponding six-coordinate [H2M(diphosphine)2]+ species. For M = Ir the bond energies of the five- and six-coordinate complexes are nearly the same and for M = Co the six-coordinate species are 1-5 kcal/mol less than the corresponding five-coordinate species. Simplified models of large and complicated ligands seem to capture the essential trends and give very good estimates of these thermodynamic properties compared with experimentally available data that are difficult to obtain. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)1993-2000
Number of pages8
JournalJournal of Physical Chemistry A
Volume121
Issue number9
DOIs
Publication statusPublished - Mar 9 2017

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Hydrides
hydrides
Transition metals
transition metals
dissociation
trends
energy
Thermodynamic properties
Ligands
Oxidation
dihydrides
thermodynamic properties
ligands
oxidation
probes
estimates

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Trends in Homolytic Bond Dissociation Energies of Five- and Six-Coordinate Hydrides of Group 9 Transition Metals : Co, Rh, Ir. / Glezakou, Vassiliki Alexandra; Rousseau, Roger; Elbert, Stephen T.; Franz, James A.

In: Journal of Physical Chemistry A, Vol. 121, No. 9, 09.03.2017, p. 1993-2000.

Research output: Contribution to journalArticle

Glezakou, Vassiliki Alexandra ; Rousseau, Roger ; Elbert, Stephen T. ; Franz, James A. / Trends in Homolytic Bond Dissociation Energies of Five- and Six-Coordinate Hydrides of Group 9 Transition Metals : Co, Rh, Ir. In: Journal of Physical Chemistry A. 2017 ; Vol. 121, No. 9. pp. 1993-2000.
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