Reactions of a neutral silyleneruthenium complex with ketones and aldehydes, and isolation of their agostic intermediates are reported, where an α-H abstraction or hydrosilylation of the carbonyl compounds occurs depending on the substituents of the substrates.

A silyl(silylene)ruthenium complex, Cp*Ru(CO)(═SiMes2)SiMe3 (2), was synthesized by the reaction of Cp*Ru(CO)(py)Me with HSiMe2SiMes2Me (Mes = 2,4,6-trimethylphenyl). In contrast to its iron analogue Cp*Fe(CO)(═SiMes2)SiMe3 (1), which we reported previously, 2 exhibits a fluxional behavior that involves rotation around the Ru═Si and Si−C(mesityl) bonds. The activation parameters for the M═Si bond rotation were determined for the first time using line-shape analysis of the variable-temperature 1H NMR spectra of 2. Complex 2 underwent a facile alkoxylation reaction on the silyl ligand with ROH (R = Me or Et) in the presence of R′NC (R′ = tBu or Xyl = 2,6-dimethylphenyl) to afford Cp*Ru(CO)(CNR′)[Si(OR)3] and Mes2Si(OR)H in high yields at room temperature, with cleavage of all three Si−C bonds.

A phosphido-bridged unsymmetrical diiron complex (η5-C5Me5)Fe2(CO)4(μ-CO)(μ-PPh2) (1) was synthesized by a new convenient method; photo-dissociation of a CO ligand from (η5-C5Me5)Fe2(CO)6(μ-PPh2) (2) that was prepared by the reaction of Li[Fe(CO)4PPh2] with (η5-C5Me5)Fe(CO)2I. The reactivity of 1 toward various alkynes was studied. The reaction of 1 with tBuCCH gave a 1:1 mixture of two isomeric complexes (η5-C5Me5)Fe2(CO)3(μ-PPh2)[μ-CHC(tBu)C(O)] (3) containing a ketoalkenyl ligand. The reactions of 1 with other terminal alkynes RCCH (R=H, CO2Me, Ph) afforded complexes incorporating one or two molecules of alkynes and a carbonyl group. The principal products were dinuclear complexes bridged by a new phosphinoketoalkenyl ligand, (η5-C5Me5)Fe2(CO)3(μ-CO)[μ-CR1CR2C(O)PPh2] (4a: R1=H, R2=H; 4b: R1=CO2Me, R2=H; 4c: R1=H, R2=Ph). In the cases of alkynes RCCH (R=H, CO2Me), dinuclear complexes having a new ligand composed of two molecules of alkynes, a carbonyl group, and a phosphido group; i.e. (η5-C5Me5)Fe2(CO)3[μ-CRCHCHCRC(O)PPh2] (5a: R=H; 5b: R=CO2Me), were also obtained. In all cases, mononuclear complexes, (η5-C5Me5)Fe(CO)[CR1CR2C(O)PPh2] (6a: R1=H, R2=H; 6b: R1=H, R2=CO2Me; 6c: R1=H, R2=Ph) were isolated in low yields. The structures of 1, 4c, 5b, and 6a were confirmed by X-ray crystallography. The detailed structures of the products and plausible reaction mechanisms are discussed.The phosphido-bridged unsymmetrical diiron complex (η5-C5Me5)Fe2(CO)4(μ-CO)(μ-PPh2) (1) was prepared by a new method. The reactions of 1 with various terminal alkynes RCCH (R=tBu, H, CO2Me, Ph) afforded complexes containing a ketoalkenyl or phosphinoketoalkenyl ligand on incorporating one or two molecules of alkynes and a carbonyl group as a result of C–C bond and P–C bond coupling.

Reactions of a neutral silyleneruthenium complex with ketones and aldehydes, and isolation of their agostic intermediates are reported, where an α-H abstraction or hydrosilylation of the carbonyl compounds occurs depending on the substituents of the substrates.