Pentacarbonylmanganese complexes of indium

Abstract

The preparation of In[Mn(CO)₅]₃, XIn[Mn(CO)₅]₂, and X₂InMn(CO)₅(X = Cl or Br) is described and their i.r. and mass spectra are discussed. The In–Mn bonds are readily cleaved by halogens and hydrogen halides to form XIn[Mn(CO)₅]₂, X₂InMn(CO)₅, or InX₃ depending on the stoicheiometry of the reactants. In acetone or methanol solution the complexes XIn[Mn(CO)₅]₂ and X₂InMn(CO)₅ undergo redistribution reactions to give In[Mn(CO)₅]₃ and InX₃. In acetonitrile solution, however, all the complexes X_3-nIn[Mn(CO)₅]_n ionise to give the cation [(MeCN)₂InMn₂(CO)₁₀]⁺ which has been isolated as its perchlorate salt. The interaction of halide ions with the indium complexes gives anionic halide derivatives such as R₄N⁺{X_4-nIn[Mn(CO)₅]_n}^–(n= 1–3; R = Me, X = Cl; R = Et, X = Br) which also ionise in acetonitrile to yield the cation [(MeCN)₂InMn₂(CO)₁₀]⁺.