The syntheses and vibrational spectra of the homoleptic metal acetonitrile cations [Au(NCCH3)(2)](+), [Pd(NCCH3)(4)](2+), [Pt(NCCH3)(4)](2+), and the adduct CH3CN.SbF5. The crystal and molecular structures of [M(NCCH3)(4)][SbF6](2).CH3CN, M = Pd or P

摘要

Solvolyses of the homoleptic metal carbonyl salts [M(CO)(4)][Sb2F11](2), M = Pd or Pt, in acetonitrile leads at 50 degrees C both to complete ligand exchange for the cations as well as to a conversion of the di-octahedral anion [Sb2F11](-) into [SbF6](-) and the molecular adduct CH3CN . SbF5 according to: [M(CO)(4)][Sb2F11](2) + 7 CH3CN --> [M(NCCH3)(4)][SbF6](2) . CH3CN + 2 CH3CN SbF5 + 4 CO M = Pd, Pt The monosolvated [M(NCCH3)(4)][SbF6](2) . CH3CN are obtained as single crystals from solution and are structurally characterized by single crystal x-ray diffraction. Both salts are isostructural. The cations are square planar but the N-C-C-sceletial groups of the ligands depart slightly from linearity. The new acetonitrile complexes as well as [Au(NCCH3)(2)][SbF6] and the adduct CH3CN . SbF5 are completely characterized by vibrational spectroscopy. [References: 27]