CHIMIA (Apr 2016)

PH3 as a Phosphorus Source for Phosphinidene–Carbene Adducts and Phosphinidene–Transition Metal Complexes

  • Mark Bispinghoff,
  • Hansjörg Grützmacher

DOI
https://doi.org/10.2533/chimia.2016.279
Journal volume & issue
Vol. 70, no. 4

Abstract

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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.

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