Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 7, Pages 1896-1900Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201309515
Keywords
hydrogenation; iridium; reaction mechanisms; reactive intermediates; structure elucidation
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Funding
- Swiss National Science Foundation
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Previously elusive iridium dihydride alkene complexes have been identified and characterized by NMR spectroscopy in solution. Reactivity studies demonstrated that these complexes are catalytically competent intermediates. Additional H-2 is required to convert the catalyst-bound alkene into the hydrogenation product, supporting an Ir-III/Ir-V cycle via an [Ir-III(H)(2)(alkene)(H-2)(L)](+) intermediate, as originally proposed based on DFT calculations. NMR analyses indicate a reaction pathway proceeding through rapidly equilibrating isomeric dihydride alkene intermediates with a subsequent slow enantioselectivity-determining step. As in the classical example of asymmetric hydrogenation with rhodium diphosphine catalysts, it is a minor, less stable intermediate that is converted into the major product enantiomer.
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