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Updated: Nov 1, 2025

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
A 2,2'-diphosphinotolane as a versatile precursor for the synthesis of P-ylidic mesoionic carbenes via reversible C-P
Hannah K Wagner1, Hubert Wadepohl1, Joachim Ballmann1
1Anorganisch-Chemisches Institut, Universität Heidelberg Im Neuenheimer Feld 276 D-69120 Heidelberg Germany joachim.ballmann@uni-heidelberg.de.
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.
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