Selective C - C vs C - H bond activation by rhodium(I) PCP pincer complexes. A computational study

Andreas Sundermann, Olivier Uzan, David Milstein, Jan M L Martin

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Abstract

A theoretical study of the oxidative addition of C - C vs C - H bonds to a rhodium(I) complex with PCP-type ligands has been carried out. Special attention has been paid to the effect of different bulky substituents at the phosphorus atoms of the chelate ligand. Therefore, B3LYP/lanl2dz+p//B3LYP/lanl2dz and ONIOM(B3LYP/lanl2dz+p:B3LYP/lanl2dz)//ONIOM(B3LYP/lanl2dz:HF/lanl 1mb) methods have been utilized. According to the calculations, C - H activation is always the kinetically favored process (ΔΔE(≠) 20 kJ·mol-1), though the C - C activation product is more stable (ΔΔE 20 kJ·mol-1). C - H addition is a reversible process; the product of the C - H activation can interconvert to the C - C activation product via an intermediate structure. Bulky substituents are found to increase the barrier for C-H activation relative to that for C - C activation. With additional ligands (e.g., phosphines), hexacoordinate complexes are formed. This is more favorable for the C - C activation products. Our calculations show that the activation reaction proceeds via complexes with a pentacoordinated rhodium atom. Thus, in the presence of donor ligands, the activation reaction is inhibited.

Original languageEnglish
Pages (from-to)7095-7104
Number of pages10
JournalJournal of the American Chemical Society
Volume122
Issue number29
DOIs
Publication statusPublished - Jul 26 2000

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Rhodium
Chemical activation
Ligands
Phosphines
Phosphorus
Theoretical Models
Atoms

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Selective C - C vs C - H bond activation by rhodium(I) PCP pincer complexes. A computational study. / Sundermann, Andreas; Uzan, Olivier; Milstein, David; Martin, Jan M L.

In: Journal of the American Chemical Society, Vol. 122, No. 29, 26.07.2000, p. 7095-7104.

Research output: Contribution to journalArticle

Sundermann, Andreas ; Uzan, Olivier ; Milstein, David ; Martin, Jan M L. / Selective C - C vs C - H bond activation by rhodium(I) PCP pincer complexes. A computational study. In: Journal of the American Chemical Society. 2000 ; Vol. 122, No. 29. pp. 7095-7104.
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