The ruthenium triflate complex Cp*(PiPr3)RuOTf (1) was generated from the reaction of Cp*(PiPr3)RuCl with Me3SiOTf in dibutyl ether. Complex 1 reacted with primary and secondary silanes to produce a family of Ru(IV) silyl dihydride complexes of the type Cp*(PiPr3)Ru(H)2(SiRR'OTf) (3 - 12). Structural analyses of complexes 8 (R = R' = Ph) and 12 (R = R' = fluorenyl) revealed the presence of a tetrahedral silicon center and a four-legged piano stool geometry about ruthenium. Anion abstraction from Cp*(PiPr3)Ru(H)2(SiHROTf) by [Et3Si*toluene][B(C6F5)4] afforded hydrogen-substituted cationic ruthenium silylene complexes [Cp*(PiPr3)Ru(H)2(=SiHR)][B(C6F5)4] (R = Mes (13), R = Si(SiMe3) (14)) that display a significant Ru - H ... Si interaction, as indicated by relatively large 2JSiH coupling constants (2JSiH = 58.2 Hz (13), 2JSiH = 37.1 Hz (14)). The syntheses of secondary silylene complexes [Cp*(PiPr3)Ru(H)2(=SiRR')][B(C6F5)4] (R = R' = Ph (15); R = Ph, R' = Me (16), R = R' = fluorenyl (17)) were also achieved by anion abstraction with [Et3Si*toluene][B(C6F5)4]. Complexes 15 - 17 do not display strong Ru - H ... Si secondary interactions, as indicated by very small 2JSiH coupling constant values.

The cationic ruthenium silylene complex [Cp*(PiPr3)Ru(H)2(SiHMes)] [CB11H6Br6], a catalyst for olefin hydrosilations with primary silanes, was isolated and characterized by X-ray crystallography. Relatively strong interactions between the silylene Si atom and Ru-H hydride ligands appear to reflect a highly electrophilic silicon center. Kinetic and mechanistic studies on hydrosilations with this catalyst reveal a fast, initial addition of the Si-H bond of the silylene complex to the olefin. Subsequent migration of a hydride ligand to silicon produces a 16-electron intermediate, which can be trapped by olefin, resulting in inhibition of catalysis, or intercepted by the silane substrate. The latter reaction pathway, involving oxidative addition of the Si-H bond and a somewhat concomitant loss of product, is the rate-determining step in the catalytic cycle.

Reactions of the cationic ruthenium silylene complexes [Cp*(PiPr3)Ru(H)2(=SiRR')][B(C6F5)4] (R = Mes, R' = H, 1; R = R' =Ph, 2) with alkenes, alkynes, ketones, and Lewis bases were explored. Addition of 1-hexene, 3,3-dimethylbut-1-ene, styrene, and cyclopentene to 1 afforded the disubstituted silylene products [Cp*(PiPr3)Ru(H)2(=SiMesR)][B(C6F5)4] (R = Hex, 3; R = CH2CH2tBu, 4; R = CH2CH2Ph, 5; R = C5H9, 6). Analogous reactions with 2-butyne and 3,3-dimethylbut-1-yne yielded the vinyl-substituted silylene complexes [Cp*(PiPr3)Ru(H)2(=Si(CR=CHR')Mes)][B(C6F)4] (R = R' = Me, 7; R = H, R' = tBu, 8). Complex 1 undergoes reactions with ketones to give the heteroatom-substituted silylene complexes [Cp*(PiPr3)Ru(H)2(=Si(OCHPhR)Mes)][B(C6F)4] (R = Ph, 9; R = Me, 10). Interestingly, complexes 3 - 8 display a weak interaction between the hydride ligands and the silicon center, while 9 and 10 exhibit a relatively large interaction (as determined by 2JSiH values). The reaction of isocyanates with 1 resulted in the silyl complexes [Cp*(PiPr3)Ru(H)2(Si(Mes)[n2-O(CH)(NC6H4R)][B(C6F5)4] (R = H, 11; R = CF3, 12), and an intermediate in this transformation is observed. Complex 2 was subjected to various Lewis bases to yield the base-stabilized silylene complexes [Cp*(PiPr3)Ru(H)2(SiPh2*L)][B(C6F)4] (L = DMAP, 13; L = Ph2CO, 14; L = PhCONH2, 15; L = NHMePh, 16, L = tBuSONH2, 18) and the reaction of 1 with NHMePh gave [Cp*(PiPr3)Ru(H)2(SiHMes*NHMePh)][B(C6F)4].

The cationic germylene complex [Cp*(PiPr3)Ru(H)2(=GeMes2)][OTf] (1) was synthesized from the reaction of Cp*(PiPr3)RuOTf with H2GeMes2, and addition of DMAP to 1 yielded the neutral germylene complex [Cp*(PiPr3)Ru(H)(=GeMes2) (2). The reaction of H3GeTrip and Cp*(PiPr3)RuCl gave the germyl complex Cp*(PiPr3)Ru(H)2(GeHTripCl) (3), which undergoes a reaction with Li(Et2O)2[B(C6F5)4] to afford the cationic H-substituted germylene complex [Cp*(PiPr3)Ru(H)2(=GeHTrip)][B(C6F5)4] (4). Addition of 1-hexene, 3,3-dimethylbut-1-ene, styrene, and allyl chloride to 4 afforded the disubstituted germylene products [Cp*(PiPr3)Ru(H)2(=GeTripR)][B(C6F5)4] (R = Hex, 5; R = CH2CH2Ph, 6; R = CH2CH2tBu, 7; R = CH2CH2CH2Cl, 8). Analogous reactions with 2-butyne and 3,3-dimethylbut-1-yne yielded the vinyl-substituted germylene complexes [Cp*(PiPr3)Ru(H)2(=Ge(CR=CHR')Trip)][B(C6F)4] (R = H, R' = tBu, 9; R = R' = Me, 10).

New di(phosphine)-supported rhodium and iridium silyl complexes were synthesized. Reactions of the di(t-butylphosphino)ethane complex (dtbpe)Rh(CH2Ph) with Ph2SiH2 and Et2SiH2 resulted in isolation of (dtbpe)Rh(H)2(SiBnPh2) (1, Bn = CH2Ph) and (dtbpe)Rh(H)2(SiBnEt2) (2), respectively. Both 1 and 2 display strong interactions between the rhodium hydride ligands and the silyl ligand, as indicated by large 2JSiH values (44.4 and 52.1 Hz). The reaction of (dtbpm)Rh(CH2Ph) (dtbpm = di(t-butylphosphino)methane) with Mes2SiH2 gave the pseudo-three-coordinate Rh complex (dtbpm)Rh(SiHMes2) (3), which is stabilized in the solid state by agostic interactions between the rhodium center and two C - H bonds of a methyl substituent of a mesityl group. The analogous germanium compound (dtbpm)Rh(GeHMes2) (4) is also accessible. Complex 3 readily undergoes reactions with diphenylacetylene, phenylacetylene, and 2-butyne to give the silaallyl complexes (dtbpm)Rh[Si(CPh=CHPh)Mes2] (5), (dtbpm)Rh[Si(CH=CHPh)Mes2] (7), and (dtbpm)Rh(Si(CMe=CHMe)Mes2) (8) via net insertions into the Si - H bond. The germaallyl complexes (dtbpm)Rh[Ge(CPh=CHPh)Mes2] (6) and (dtbpm)Rh[Ge(CMe=CHMe)Mes2] (9) were synthesized under identical conditions starting from 4. The reaction of (dtbpm)Rh(CH2Ph) with 1 equiv of TripPhSiH2 yielded (dtbpm)Rh(H)2[5,7-diisopropyl-3-methyl-1-phenyl-2,3-dihydro-1H-silaindenyl-kSi] (11), and catalytic investigations indicate that both (dtbpm)Rh(CH2Ph) and 11 are competent catalysts for the conversion of TripPhSiH2 to 5,7-diisopropyl-3-methyl-1-phenyl-2,3-dihydro-1H-silaindole. A dtbpm-supported Ir complex, [(dtbpm)IrCl]€2, was used to access the dinuclear bridging silylene complexes [(dtbpm)IrH](SiPh2)(Cl)2[(dtbpm)IrH] (12) and [(dtbpm)IrH](SiMesCl)(-Cl)(H)[(dtbpm)IrH] (13). The reaction of [(dtbpm)IrCl]2 with a sterically bulky primary silane, (dmp)SiH3 (dmp = 2,6-dimesitylphenyl), allowed isolation of the mononuclear complex (dtbpm)Ir(H)4(10-chloro-1-mesityl-5,7-dimethyl-9,10-dihydrosilaphenanthrene-Si) (14), in which the dmp substituent has undergone C-H activation.

The dichloride complex Cp*(Am)WCl2 (1, Am = [(iPrN)2CMe]-) reacted with the primary silanes PhSiH3, (p-tolyl)SiH3, (3,5-xylyl)SiH3, and (C6F5)SiH3 to produce the W(VI) (silyl)trihydrides Cp*(Am)W(H)3(SiHPhCl) (2), Cp*(Am)W(H)3(SiHTolylCl) (3), Cp*(Am)W(H)3(SiHXylylCl) (4), and Cp*(Am)W(H)3[SiH(C6F5)Cl] (5). In an analogous manner, 1 reacted with PhSiH2Cl to give Cp*(Am)W(H)3(SiPhCl2) (6). Complex 6 can alternatively be quantitatively produced from the reaction of 2 with Ph3CCl. NMR spectroscopic studies and X-ray crystallography reveal an interligand H...Si interaction between one W - H and the chlorosilyl group, which is further supported by DFT calculations.

Complexes of Ru(II) containing the pincer ligand [-N(2-PPh2-4-Me-C6H3)2] (PNPPh) were prepared. The complex (PNPPhH)RuCl2 (1) was treated with 2 equiv AgOTf to produce the triflate complex (PNPPhH)Ru(OTf)2 (2). Complex 1 was also treated with an excess of NaBH4 to give a bimetallic complex [(PNPPh)RuH3]2 (3). A number of methods, including X-ray crystallography, NMR spectroscopy, and computational studies, were used to probe the structure of 3. Addition of Lewis bases to 3 resulted in octahedral complexes containing a hydride ligand trans to a dihydrogen ligand.