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Issue 11, 2000
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An unexpected electronic preference for transfer of a β-hydrogen trans to a metal–hydride bond

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Abstract

Density functional calculations (R = H) on the decomposition of cis-mer-HIr(OCH3)Cl(PR3)3 to cis-mer-(H)2IrCl(PR3)3 [italic v (to differentiate from Times ital nu)]ia a β-H transfer process are reported. The favoured computed pathway involves transfer of a β-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 β-H transfer process involves rearrangement of a π-stabilised unsaturated alkoxide intermediate with the preferred pathway being favoured by reduced interactions between trans ligands in the resultant pseudo square-pyramidal transition state.

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Publication details

The article was received on 03 Aug 2000 and first published on 06 Oct 2000


Article type: Paper
DOI: 10.1039/B006546N
Citation: New J. Chem., 2000,24, 855-858
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    An unexpected electronic preference for transfer of a β-hydrogen trans to a metal–hydride bond

    S. A. Macgregor and B. Sweeney, New J. Chem., 2000, 24, 855
    DOI: 10.1039/B006546N

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