An unexpected electronic preference for transfer of a β-hydrogen trans to a metal-hydride bond

S. A. Macgregor, B. Sweeney

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Density functional calculations (R = H) on the decomposition of cis-mer-HIr(OCH3)Cl(PR3)3 to cis-mer-(H)2IrCl(PR3)3 via a ß-H transfer process are reported. The favoured computed pathway involves transfer of a ß-H to a site trans to the Ir-H bond and is consistent with that deduced experimentally (R = Me, Et). Unexpectedly however, and in contrast to earlier calculations on analogous systems, this pathway is shown to be preferred on electronic grounds and not only on steric grounds as previously thought. The ß-H transfer process involves rearrangement of a p-stabilised unsaturated alkoxide intermediate with the preferred pathway being favoured by reduced interactions between trans ligands in the resultant pseudo square-pyramidal transition state.

Original languageEnglish
Pages (from-to)855-858
Number of pages4
JournalNew Journal of Chemistry
Volume24
Issue number11
DOIs
Publication statusPublished - 2000

Fingerprint Dive into the research topics of 'An unexpected electronic preference for transfer of a β-hydrogen trans to a metal-hydride bond'. Together they form a unique fingerprint.

Cite this