An unprecedented reaction via consecutive trans-selective hydrosilylation and o-C−H silylation of arylalkynes with hydrosilanes was developed by use of ruthenium complex catalysts Ru{κ 3 (Si,O,Si)-xantsil}-(CO)(PR 3 ) (R = NC 4 H 8 (1-Pyrr), NC 5 H 10 (1-Pip); xantsil = (9,9dimethylxanthene-4,5-diyl)bis(dimethylsilyl)). This reaction proceeded with gentle heating at 40−60 °C and afforded novel 2,α-bis-silylated (Z)-stilbene or (Z)-styrene derivatives 2 together with an equimolar amount of (E)-/(Z)arylalkenes as byproducts. The selectivity of the formation of 2 reached a maximum by employing catalyst 1-Pyrr ligated by the less bulky triaminophosphine P(NC 4 H 8 ) 3 and hydrosilane HSiMe(OSiMe 3 ) 2 having moderately bulky and electron withdrawing substituents.

Photoinduced decarbonylation of Cp*M(CO)(3)Me (M = Mo and W, Cp* = η(5)-C(5)Me(5)) in the presence of xantsilH(2) [xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)] in pentane gave bis(silyl)hydrido complexes Cp*M(κ(2)Si,Si-xantsil)(CO)(2)(H) (1a: M = Mo and 1b: M = W) through two-fold Si-H oxidative addition and methane elimination. Further irradiation of 1a,b in toluene afforded tridentate xantsil complexes Cp*M(κ(3)Si,Si,O-xantsil)(CO)(H) (2a: M = Mo and 2b: M = W) via CO dissociation. Reactions of complexes 2a,b with nitriles led to stoichiometric hydrosilylation at the C[triple bond, length as m-dash]N triple bond. Thus, reaction of 2a,b with t-BuCN at room temperature afforded N-silyliminoacyl complexes 3a,b, through insertion of a nitrile into the M-Si bond, and the products slowly isomerised to the corresponding N-silylimine complexes 4a,bvia intramolecular hydrogen migration. On the other hand, reaction of 2a,b with PhCN afforded N-silylimine complexes 5a,b directly. The molecular structures of 1a, 3a and 5b were determined by X-ray crystallography, revealing that complex 3a has a 3-centre-2-electron (3c-2e) Mo-Si-H bond.