Terminal, electrophilic phosphinidene complexes (M=PR) are attractive platforms for PR-transfer to organic substrates. In contrast to aryl- or alkylphosphinidene complexes terminal chlorophosphinidenes (M=PCl) have only been proposed as transient intermediates but isolable example remain elusive. Here we present the transfer of PCl from chloro-substituted dibenzo-7λ3-phosphanorbornadiene to a square-planar osmium(II) PNP pincer complex to give the first isolable, terminal chlorophosphinidene complex with remarkable thermal stability. Os=P bonding was examined computationally giving rise to highly covalent {OsII=PICl} double bonding.
Keywords: Density functional calculations; Natural localized molecular orbital (NLMO); Osmium; Phosphinidene; Pincer.
© 2020 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA.