Preparation of silanediyl-bridged Fe-Fe and Fe-W dinuclear complexes. X- ray structures of [Cp*Fe(Co)(μ-CO) {μ-Si(H)CHPH2}(CO)(n)MCp] (Cp* = C5Me5, Cp = C5H5, M = Fe, n = 1; M = W, n = 2)

Article abstract of DOI:10.1246/bcsj.71.2865

Photolysis of a 2:1 mixture of [Cp*Fe(CO)₂Me] and Ph₂CHSiH₃ produces mainly the mononuclear silyl complex [Cp*Fe(CO)2{Si(H)₂CHPh₂}] (1) together with two silanediyl-bridged diiron complexes: cis- and trans- [Cp*₂(CO)₂Fe₂(μ-CO){μ-Si(H)CHPh₂}] (2), and [{Cp*Fe(CO)₂}₂]. The trans-2 complex isomerizes to cis-2 photochemically, but no cis-trans isomerization occurs thermally below 100°C. Photolysis of [CpFe(CO)₂SiMe₃] or [CpW(CO)₃Me] in the presence of 1 produces novel silanediyl-bridged complexes [Cp*Fe(CO)(μ-CO){μ-Si(H)CHPh₂}(CO)(n)MCp] (3: M = Fe, n = 1; 4: M = W, n = 2) in moderate yields. Complexes 3 and 4 have been characterized by X-ray diffraction analysis. To the best of our knowledge, complex 4 is the first example of a silanediyl-bridged Fe-W complex. The Cp and Cp* rings are mutually cis with the dihedral angle of 78.7(2)°in complex 3, but they are trans with the dihedral angle of 13.1(6)°in complex 4.