Selective carbon-carbon bond activation of epoxides by a bisphosphine Pt(0) complex
Contrasting established bond activation chemistry of oxiranes (epoxides), the unprecedented insertion of a Pt(0) complex into the carbon-carbon bonds of ethylene oxide and other epoxides, generating 3-oxaplatinacyclobutanes under remarkably mild conditions, has been found. Pt(II) neopentyl hydride c...
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| Main Authors: | , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
28 August 2019
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| In: |
Organometallics
Year: 2019, Volume: 38, Issue: 17, Pages: 3358-3368 |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/acs.organomet.9b00450 |
| Online Access: | Verlag, Volltext: https://doi.org/10.1021/acs.organomet.9b00450
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| Author Notes: | Susanne Neumann, Thomas W. Gerl, Frank Rominger, Gunter Scherhag, Claudia Meier, Markus Metz, Alberto Albinati, and Peter Hofmann |
| Summary: | Contrasting established bond activation chemistry of oxiranes (epoxides), the unprecedented insertion of a Pt(0) complex into the carbon-carbon bonds of ethylene oxide and other epoxides, generating 3-oxaplatinacyclobutanes under remarkably mild conditions, has been found. Pt(II) neopentyl hydride complex (dtbpm-κ2P)Pt(Np)H (1) undergoes first-order reductive elimination of neopentane at ambient temperature in solution, forming a highly reactive species of an overall composition [(dtbpm)Pt(0)] (C). This intermediate inserts into epoxide C-C bonds or, in the absence of substrates, dimerizes to d10-d10 Pt(0) species D. The epoxide activation products have been fully characterized including X-ray structure determinations. Various experiments have been conducted in order to decipher mechanistic details of this unusual chemistry. Theoretical studies on various levels do not allow a reliable conclusion as to the actual nature of the reactive intermediate C. Both conceivable structures C1 (ring-opened [(dtbpm-κ1P)Pt(0), d10-ML, 12 VE]) and C2 (chelate, [(dtbpm-κ2P)Pt(0)], d10-ML2, 14 VE) are minimum-energy structures with a very small (method-dependent) energy difference. |
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| Item Description: | Gesehen am 07.10.2019 |
| Physical Description: | Online Resource |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/acs.organomet.9b00450 |