Open AccessPH3 as a Phosphorus Source for Phosphinidene–Carbene Adducts and Phosphinidene–Transition Metal Complexes
Author(s) -
Mark Bispinghoff,
Hansjörg Grützmacher
Publication year - 2016
Publication title -
chimia
Language(s) - English
Resource type - Journals
eISSN - 2673-2424
pISSN - 0009-4293
DOI - 10.2533/chimia.2016.279
Subject(s) - phosphinidene , steric effects , synthon , adduct , chemistry , carbene , transition metal , main group element , reactivity (psychology) , medicinal chemistry , photochemistry , stereochemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
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.