Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 12, Pages 3217-3221Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201712791
Keywords
density-functional calculations; platinum; silane; structure elucidation; x-ray diffraction
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Funding
- MINECO [CTQ2016-76267-P, CTQ2017-87889-P, CTQ2016-81797-REDC]
- Junta de Andalucia [FQM-2126]
- Junta de Andalucia
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The platinum complex [Pt((IBuPr)-Bu-t-Pr-i')((IBuPr)-Bu-t-Pr-i)][BArF] interacts with tertiary silanes to form stable (<0 degrees C) mononuclear Pt-II sigma-SiH complexes [Pt((IBuPr)-Bu-t-Pr-i')((IBuPr)-Bu-t-Pr-i)(eta(1)-HSiR3)][BArF]. These compounds have been fully characterized, including X-ray diffraction methods, as the first examples for platinum. DFT calculations (including electronic topological analysis) support the interpretation of the coordination as an unusual eta(1)-SiH. However, the energies required for achieving a eta(2)-SiH mode are rather low, and is consistent with the propensity of these derivatives to undergo Si-H cleavage leading to the more stable silyl species [Pt(SiR3)((IBuPr)-Bu-t-Pr-i)(2)]-[BArF] at room temperature.
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