A convenient method for the generation of {Rh(PNP)} + and {Rh(PONOP)} + fragments: Reversible formation of vinylidene derivatives

Abstract

The substitution reactions of [Rh(COD) 2 ][BAr F4 ] with PNP and PONOP pincer ligands 2,6-bis(di-tert-butylphosphinomethyl)pyridine and 2,6-bis(di-tert-butylphosphinito)pyridine in the weakly coordinating solvent 1,2-F 2 C 6 H 4 are shown to be an operationally simple method for the generation of reactive formally 14 VE rhodium(i) adducts in solution. Application of this methodology enables synthesis of known adducts of CO, N 2 , H 2 , previously unknown water complexes, and novel vinylidene derivatives [Rh(pincer)(CCHR)][BAr F4 ] (R = tBu, 3,5-tBu 2 C 6 H 3 ), through reversible reactions with terminal alkynes.