Abstract
Reactions of PH-substituted phosphinidene–imidazolylidenes with I2 afford isolable NHC-adducts of the transient diiodophosphine PHI2. The products, which show a surprising structural diversity, are according to DFT studies best formulated as charge-transfer complexes of onio-substituted cationic phosphines with I− and are capable of reaction under formal transfer of an NHC-P+ unit.