Bis(dimethylgermyl)alkane-iron tetracarbonyls: Synthesis, photolysis, and reactivity

Article abstract of DOI:10.1021/om00109a001

This work concerns the synthesis, spectroscopic analysis, and reactivity of tetracarbonyliron bis(dimethylgermyl)alkanes Me₂Ge(CH₂)_nGe(Me₂)Fe(CO)₄ (n = 1, 2). These heterocycles are obtained by cyclization of bis(dimethylgermyl)alkanes Me₂HGe(CH₂)_nGeHMe₂ (n = 1, 2) with Fe(CO)₅ under UV irradiation. They are stable at room temperature, but the heterocycle with n = 1 decomposes under prolonged UV irradiation with formation of the heterocycle with n = 2, perhydrotetragermin, and (CO)₃Fe(μ-GeMe₂)₃Fe(CO)₃. Various CO substitution reactions with phosphines and cleavage reactions with organic and organometallic halides are described; they provide a convenient procedure for the generation of germanium or tin-carbonyl iron clusters. Reactions of tetracarbonyliron bis(dimethylgermyl)methane with sulfur and with oxygen presumably lead first to the dithia- (or dioxa-) digermolane Me₂GeCH₂Ge(Me₂)Y-Y (Y = S or O) and after, by sulfur (or oxygen) loss, to thia- (or oxa-) digermetane Me₂GeCH₂GeMe₂Y (Y = S or O), which are unstable, giving products suggestive of Me₂GeY (Y = O or S) and Me₂Ge=CH₂ intermediates.