Facile halide replacement in electron rich complexes

Reactions of MnL₅X or Mn(CO)L₄X compounds (L = several aryl isocyanides, X = halide) with AgPF₆ give MnL₆]PF₆ or Mn(CO)L₅]PF₆ respectively. These reactions are presumed to occur with initial halide extraction to give an intermediate solvated species MnL₅solv]⁺ or Mn(CO)L₄solv]⁺ which can subsequently decompose or scavenge free L from solution to give the products observed. Addition of an alternative potential ligand L′ allows preparation of mixed ligand species MnL₅L′]PF₆ or Mn(CO)L₄L'‵PF₆ (L = MeNC, ^tBuNC, py). Cyclic voltammetric studies on the various complexes have been carried out, and results correlated with infrared data and with theory.