Synthesis and Reactivity of N‑Heterocyclic Carbene Coordinated Formal Germanimidoyl-Phosphinidenes

Treatment of N-heterocyclic carbene (NHC) ligated germylidenylphosphinidene MsFluid tBu-GeP­(NHC iPr) (where MsFluid tBu is a bulky hydrindacene substituent, and NHC iPr is 1,3-diisopropyl-4,5-dimethyl-imidazolin-2-ylidene) with mesityl azide and 4-tertbutylphenyl azide afforded NHC coordinated formal germanimidoyl-phosphinidenes, which represent the first compounds bearing both GeN double bond and phosphinidene functionalities. Studies of the chemical properties revealed that the reactions preferred to occur at the GeN double bond, which underwent [2 + 2] cycloadditions with CO2 and ethyl isocyanate, and coordinated with coinage metals through the nitrogen atom.