A 2,2′-diphosphinotolane as a versatile precursor for the synthesis of P-ylidic mesoionic carbenes via reversible C–P bond formation
Open Access
- 29 January 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Chemical Science
- Vol. 12 (10), 3693-3701
- https://doi.org/10.1039/d0sc06128j
Abstract
A metal-templated synthetic route to cyclic (aryl)(ylidic) mesoionic carbenes (CArY-MICs) featuring an endocyclic P-ylide is presented. This approach, which requires metal templates with two cis-positioned open coordination sites, is based on the controlled cyclisation of a P,P′-diisopropyl-substituted 2,2′-diphosphinotolane (1) and leads to chelate complexes coordinated by a phosphine donor and the CArY-MIC carbon atom. The C–P bond formation involved in the former partial cyclisation of 1 proceeds under mild conditions and was shown to be applicable all over the d-block. In the presence of a third fac-positioned open coordination site, the P–C bond formation was found to be reversible, as shown for a series of molybdenum complexes. DFT modelling studies are in line with an interpretation of the target compounds as CArY-MICs.Funding Information
- Deutsche Forschungsgemeinschaft (BA 4859/2, INST 40/467-1 FUGG)
- Baden-Württemberg Stiftung
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