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Lookup NU author(s): Dr Keith Izod, Salima El-Hamruni, Dr Ross Harrington, Dr Ulrich Baisch
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N-Heterocyclic carbenes and their heavier homologues are, in part, stabilized by delocalization of the N lone pairs into the vacant p-orbital at carbon (or a heavier Group 14 element center). These interactions are usually absent in the corresponding P-substituted species, owing to the large barrier to planarization of phosphorus. However, judicious selection of the substituents at phosphorus has enabled the synthesis of a diphosphagermylene, [(Dipp)(2)P](2)Ge, in which one of the P centers is planar (Dipp = 2,6-diisopropylphenyl). The planar nature of this P center and the correspondingly short P-Ge distance suggest a significant degree of P-Ge multiple bond character that is due to delocalization of the phosphorus lone pair into the vacant p-orbital at germanium. DFT calculations support this proposition and NBO and AIM analyses are consistent with a Ge-P bond order greater than unity.
Author(s): Izod K, Rayner DG, El-Hamruni SM, Harrington RW, Baisch U
Publication type: Article
Publication status: Published
Journal: Angewandte Chemie International Edition
Year: 2014
Volume: 53
Issue: 14
Pages: 3636-3640
Print publication date: 03/03/2014
ISSN (print): 1433-7851
ISSN (electronic): 1521-3773
Publisher: Wiley - V C H Verlag GmbH & Co. KGaA
URL: http://dx.doi.org/10.1002/anie.201308002
DOI: 10.1002/anie.201308002
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