Abstract
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.
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