Cyanide-bridged dinuclear complexes: Synthesis, characterization and crystal structures

Eight dinuclear cyanide-bridged compounds with M-CN-M′ arrays with triflate anion [Cp(dppe)FeCNMnII(PY5)](OTf)2 (1a) (dppe = bis(diphenylphosphino)ethane), [Cp(dppe)FeCNZnII(PY5)](OTf)2 (2), [Cp(dppe)FeCNMnII(PY5-OH))](OTf)2 (3), [Cp(dppe)FeCNZnII(PY5-OH))](OTf)2 (4), [Cp(PPh3)2RuCNMnII(PY5)](OTf)2 (5) (PPh3 = triphenylphosphine), Cp(PPh3)2RuCN-ZnII(PY5)](OTf)2 (6), [Cp(PPh3)2RuCNMnII(PY5-OH))](OTf)2 (7) and [Cp(PPh3)2RuCNZnII(PY5-OH))](OTf)2 (8)) (PY5 = 2,6-bis-((2-pyridyl)methoxymethane)pyridine, PY5-OH = 2,6-bis(bis(2-pyridyl)carbinol)pyridine, OTf = CF3SO3−) were synthesized by the reaction of Cp(dppe)FeCN or Cp(PPh3)2RuCN with [MII(PY5-OH)(MeOH)](OTf)2 or [MII(PY5)(MeOH)](OTf)2 (MII = Zn, Mn), whereas the complex [Cp(dppe)FeCNMnII(PY5)](PF6)2 (1b) was obtained by adding Cp(dppe)FeCN to the acetonitrile solution of a mixture of Mn(CH3COO)3 and 2,6-bis(bis(2-pyridyl)methoxymethane)-pyridine. All the compounds were characterized by elemental analyses, infrared spectra, electronic absorption spectroscopy measurements, electrochemical measurements. The structures of 1a, 1b, 2, 5, 7 and 8 were determined by the single crystal X-ray diffraction. The electrochemical measurement results suggest that all the compounds were unstable when they were oxidized in solution.

Nine dinuclear cyanide-bridged compounds with M-CN-M′ arrays have been synthesized. All the compounds were characterized by infrared spectra, electronic absorption spectroscopy and electrochemistry. Six crystal structures of the compounds have been determined by X-ray diffractometry. The electrochemical results suggest that all the compounds were unstable when they were oxidized in solution.Figure optionsDownload as PowerPoint slide