A 2,2′-diphosphinotolane as a versatile precursor for the synthesis of P-ylidic mesoionic carbenes via reversible C-P bond formation
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-substitu...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
29 Jan 2021
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| In: |
Chemical science
Year: 2021, Volume: 12, Issue: 10, Pages: 3693-3701 |
| ISSN: | 2041-6539 |
| DOI: | 10.1039/D0SC06128J |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/D0SC06128J Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2021/sc/d0sc06128j 
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| Author Notes: | Hannah K. Wagner, Hubert Wadepohl and Joachim Ballmann |
| Summary: | 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. |
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| Item Description: | Gesehen am 06.08.2021 |
| Physical Description: | Online Resource |
| ISSN: | 2041-6539 |
| DOI: | 10.1039/D0SC06128J |