The novel bis(ferrio)silanols [Cp(OC)2Fe]2Si(X)OH [X = H (2), OH (4), Cl (7)] are obtained via hydrolysis of [Cp(OC)2Fe]2Si(H)Cl (1) or via oxygenation of the bis(ferrio)hydridosilanes [Cp(OC)2Fe]2Si(H)X [X = Cl (1), H (6)] with dimethyldioxirane. Subsequent condensation reactions with chlorodimethylsilane yield the bis(ferrio)siloxanes [Cp(OC)2Fe]2Si(X)(OSiMe2H) [X = H (12), OSiMe2H (13), OH (15)]. In an analogous manner the hetero-bismetalated silanol [Cp(OC)2Fe][Cp(OC)2(Me3P)W]Si(Me)OH (11) and the disiloxane [Cp(OC)2Fe][Cp(OC)2(Me3P)W]Si(Me)(OSiMe2H) (14) have been prepared. The influence of the transition metal substituents on the chemical and spectroscopic properties of these compounds has been investigated. The X-ray structure analyses of the bis(ferrio)silanol [Cp(OC)2Fe]2Si(H)OH and the bis(ferrio)dimethoxysilane [Cp(OC)2Fe]2Si(OCH3)2 (5)generated via methanolysis of [Cp(OC)2Fe]2SiCl2 (3)are presented.

The first tris-metalated silane, [(μ2-CO)Cp2(OC)2Fe2][Cp(OC)2Fe]SiH, was prepared via photoreaction of Cp(OC)2Fe−CH3 with the bis(ferrio)silane [Cp(OC)2Fe]2SiH2.

The mu2-silylene-bridged iron complexes [Cp(OC)(2)Fe](2)SiX(2) (X = F (2), Br (4), I (5)) have been prepared from the mu2-SiH(2) functional precursor [Cp(OC)(2)Fe](2)SiH(2) (1) by hydrogen/halogen exchange, using HBF(4), CBr(4), and CH(2)I(2), respectively. The fluoro- and bromo-substituted derivatives 2 and 4 are converted upon UV irradiation to the carbonyl- and dihalosilylene-bridged dinuclear complexes [Cp(OC)Fe](2) (mu2-CO)(mu2-SiX(2)) (X = F (6), Br (7)) via CO elimination. All new compounds have been characterized spectroscopically, and, in addition, the molecular structure of 2, 4, and the previously reported chloro derivative [Cp(OC)(2)Fe](2)SiCl(2) (3) has been determined by single-crystal X-ray diffraction methods. For 1-5, the Fourier transform infrared and Raman spectra have been recorded and discussed, together with density functional theory calculations, which support the experimental results of the structural and vibrational analysis. The computed geometries, harmonic vibrational wavenumbers, and their corresponding Raman scattering activities are in good agreement with the experimental data. A significant dependence of the CO and Fe-Si stretching modes on the X substituents of the mu2-silylene bridge has been observed and discussed.

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