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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Hauptverfasser: Wagner, Hannah (VerfasserIn) , Wadepohl, Hubert (VerfasserIn) , Ballmann, Joachim (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 29 Jan 2021
In: Chemical science
Year: 2021, Jahrgang: 12, Heft: 10, Pages: 3693-3701
ISSN:2041-6539
DOI:10.1039/D0SC06128J
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/D0SC06128J
Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2021/sc/d0sc06128j
Volltext
Verfasserangaben:Hannah K. Wagner, Hubert Wadepohl and Joachim Ballmann
Beschreibung
Zusammenfassung: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.
Beschreibung:Gesehen am 06.08.2021
Beschreibung:Online Resource
ISSN:2041-6539
DOI:10.1039/D0SC06128J