Triphosphiranes as phosphinidene-transfer agents - synthesis of regular and chelating NHC phosphinidene adducts

In this contribution we describe the general use of aryl-substituted triphosphiranes (Ar₃P₃; Ar = Mes, Dip, Tip) as phosphinidene transfer reagents towards N-heterocyclic carbenes (NHCs) to give a library of twelve N-heterocyclic carbene phosphinidene adducts of the type ArPNHC (NHCPs), in which the NHCs have varying steric profiles, allowing a systematic evaluation of their structural and NMR-spectroscopic properties. In the next series of experiments we utilized 1,3- and 1,4-phenylene bridged bis-NHCs to access a new class of chelating bis(NHCP)s, of which three derivatives could be structurally characterized. The 1,4-phenylene derivatives were shown to be susceptible to P-C_NHC bond cleavage when irradiated with an LED (396 nm), providing a rare example of phosphinidene release from NHCPs. The coordination chemistry of 1,3-phenylene bridged bis(NHCP)s towards GeCl₂(dioxane) and GaI₃ was investigated and revealed the formation of ion-separated cationic complexes, with significant charge transfer from the ligand to the metal center according to NBO analyses.