NHCs as Neutral Donors towards Polyphosphorus Complexes

Abstract

The first adducts of NHCs (=N-heterocyclic carbenes) with aromatic polyphosphorus complexes are reported. The reactions of [Cp*Fe(η5-P5)] (1) (Cp*=pentamethyl-cyclopentadienyl) with IMe (=1,3,4,5-tetramethylimidazolin-2-ylidene), IMes (=1,3-bis(2,4,6-trimethylphenyl)-imidazolin-2-ylidene) and IDipp (=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) led to the corresponding neutral adducts which can be isolated in the solid state. However, in solution, they quickly undergo a dissociative equilibrium between the adduct and 1 including the corresponding NHC. The equilibrium is influenced by the bulkiness of the NHC. [Cp′′Ta(CO)2(η4-P4)] (Cp′′=1,3-di-tert-butylcyclopentadienyl) reacts with IMe under P atom abstraction to give an unprecedented cyclo-P3-containing anionic tantalum complex. DFT calculations shed light onto the energetics of the reaction pathways.