Photolysis of solutions of M(CO)(6) (M) Cr, Mo, and W) in the presence of Et3SiH affords the silane complexes Cr(CO)(5)(eta(2)-HSiEt3), Mo(CO)(5)(eta(2)-HSiEt3), and W(CO)(5)(eta(2)-HSiEt3). Observed values of J(SiH) in these complexes are consistent with modest elongation of the Si-H bond. With Ph3SiH, complexes of Cr(CO)(5) and W(CO)(5) were obtained, but no complex with Mo was observed. When Ph2SiH2 was employed, only one Si-H bond interacts with the metal center. A dynamic exchange process observable on the magnetic resonance time scale exchanges the pendant and coordinated Si-H bonds of the coordinated diphenylsilane. Silanes bound to M(CO)(5) are activated with respect to reaction with nucleophiles. With methanol, catalytic methanolysis of HSiEt3 has been observed in the presence of Cr(CO)(5)(eta(2)-HSiEt3), affording Et3SiOMe.