A Terminal Chlorophosphinidene Complex

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‐7λ(3)‐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 {Os(II)=P(I)Cl} double bonding.