Iron-catalyzed dehydrogenative coupling of tertiary silanes and the reactivity of intermediates

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We found photoreaction of tertiary silanes R3SiH in DMF to produce the corresponding disiloxanes R_3Si-O-SiR_3. The consideration of catalytic reaction pathway revealed a hydridodisilyliron (IV) complex is an intermediate. In addition, unprecedented hydridoiron (IV) complexes with two different Group 14 element ligands Cp(CO)Fe(H)(EEt_3)(E'Et_3)(E, E'=Si, Ge, Sn) were isolated and characterized. The reaction of these complexes with Et_3E''H revealed the tendency of reductive elimination of Et_3EH from the central iron.