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The parent phosphinidene-carbene adduct NHC=PH is a versatile synthon in main group chemistry and can act as an electronically flexible ligand for transition metals. Previously, it could only be synthesized with sterically demanding N-aryl substituents. This paper describes simple methods for the synthesis of NHC=PH adducts with varying steric demand from elemental phosphorus or easily accessible phosphorus sources. Furthermore, the reactivity of NHCs towards PH3 was investigated. It was shown how a NHC inserts into the P-H bond of PH3, which opens up a route to NHC=PH adducts from an imidazolium salt and PH3. The adducts were used in the simple syntheses of bis(phosphinidene) mercury(II) and group 6 pentacarbonyl parent phosphinidene complexes. Their electronic and structural properties were investigated to elucidate the influence of the NHC on the phosphinidene and identify possible applications.
Bispinghoff et al. (Thu,) studied this question.