Reactions of Phenylsilanes with Iron Nonacarbonyl

Reaction of equimolar amounts of Fe₂(CO)₉ and SiPhH₃ yields the triply bridged diiron complex [(OC)₃Fe]₂(μ-SiPhH)₂(μ-CO) (1a). The analogous reaction of Fe₂(CO)₉ and SiPh₂H₂ provides the singly bridged diiron complex [(OC)₄Fe−Fe(CO)₃(SiHPh₂)](μ-η²-H-SiPh₂) (4). When 4 is photolyzed for 12 h, the complex [(OC)₃Fe]₂(μ-η²-H-SiPh₂)₂ (5) is obtained. Both 4 and 5 exhibit agostic Fe−H−Si interactions. Reaction of Fe₂(CO)₉ or Fe(CO)₅ with the disiloxane Ph₂HSi−O−SiHPh₂ gives the singly bridged diiron complex [(OC)₄Fe]₂(μ-η²-Ph₂Si−O−SiPh₂) (6). All compounds have been characterized by ¹H, ¹³C, and ²⁹Si NMR and IR spectroscopy. Compounds 4−6 have been characterized by X-ray crystallography.