Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

Reaction of carbene‐stabilized disilicon ( 1 ) with Fe(CO) 5 gives the 1:1 adduct L:SiSi[Fe(CO) 4 ]:L (L:=C{N(2,6‐Pr i 2 C 6 H 3 )CH} 2 ) ( 2 ) at room temperature. At raised temperature, however, 2 may react with another equivalent of Fe(CO) 5 to give L:Si[μ‐Fe 2 (CO) 6 ](μ‐CO)Si:L ( 3 ) through insertion of both CO and Fe 2 (CO) 6 into the Si 2 core, which represents the first experimental realization of transition metal‐carbonyl‐mediated cleavage of a SiSi double bond. The structures and bonding of both 2 and 3 have been investigated by spectroscopic, crystallographic, and computational methods.