Bypassing a highly unstable frustrated Lewis pair: dihydrogen cleavage by a thermally robust silylium-phosphine adduct

The thermally robust silylium complex [iPr3Si-PtBu3](+)[B(C6F5)4](-) (1) activates H2/D2 at 90 °C (PhCl); no evidence for dissociation into the separated Lewis pair is found. DFT calculations show H2 cleavage proceeds via Si-P bond elongation to form an encounter complex directly from the adduct, th...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2014-01, Vol.50 (84), p.12753-12756
Main Authors: Herrington, Thomas J, Ward, Bryan J, Doyle, Laurence R, McDermott, Joe, White, Andrew J P, Hunt, Patricia A, Ashley, Andrew E
Format: Article
Language:English
Subjects:
Adducts
Bypasses
Chemical bonds
Cleavage
Elongation
Encounters
Mathematical analysis
Robustness
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Summary:The thermally robust silylium complex [iPr3Si-PtBu3](+)[B(C6F5)4](-) (1) activates H2/D2 at 90 °C (PhCl); no evidence for dissociation into the separated Lewis pair is found. DFT calculations show H2 cleavage proceeds via Si-P bond elongation to form an encounter complex directly from the adduct, thus avoiding the non-isolable iPr3Si(+)-PtBu3 FLP.
ISSN:1359-7345
1364-548X
DOI:10.1039/c4cc05905k