A Ti₂Ru₂Pd₂ Oxo−Sulfido Cluster Synthesized by Linking Two Rationally Preorganized TiRuPdS₂ Heterotrimetallic Units with an Oxo Ligand:  Its Reaction with an Alkyne

Synthesis of a Sulfido- and Thiolato-Bridged Trinuclear Bimetallic Cluster [{(η5-C5Me5)Ir}2{(η5-C5H5)Ru}Cl(μ3-S)(μ2-SCH2CH2CN)2] and Its Reactions with CO, Isocyanide, and Alkyne

“…For the Ru−C(35)C(34)−S(1) linkage, the C(34)−C(35) bond length at 1.401(8) Å is intermediate between the typical C−C single and double-bond distances and comparable to those in the π-bonded alkenethiolato ligands in, for example, [Cp*Ir{μ,η 3 -SC(Me)CHCH 2 COMe}] 2 [BF 4 ] 2 (1.392(9) Å) and [(Cp*Ru) 2 (CpTi) 2 Pd 2 (PPh 3 )(μ 3 -S) 3 (μ 2 -O){μ 3 -SC(COOMe)CCOOMe}] ( 7 ; 1.401(9) Å) . The Ru−C(35) and S(1)−C(34) distances of 2.082(9) and 1.78(1) Å in 6 are not exceptional; neither are those for the Ru−C and S−C single bonds.…”

“…It is to be noted that insertion of alkynes into the M-µ 3 -S bond has been rarely observed: the precedented examples are 7 obtained from the reaction of [(Cp*Ru) 2 (CpTi) 2 Pd 2 (PPh 3 )(µ 3 -S) 4 (µ 3 -O)(µ-H) 2 ] with DMAD 18 and [Cp*MFe 3 (µ 3 -S){µ 3 -CHdC(R)S}(CO) 6 (µ 3 -CCPh)] (M ) Mo, W; R ) Ph, n Bu) or [Cp*MFe 3 (µ 3 -S)-{µ 3 -CFCdC(H)S}(CO) 7 (µ 3 -CCPh)] (M ) Mo, W) from Fe 3 S 2 (CO) 9 , Cp*M(CtCPh), and HCtCR (R ) Ph, n Bu, Fc; Fc ) ferrocenyl). 19 A related structure has also been demonstrated for the µ 4 -SCRdCR′ ligand in [Os 4 (CO) 12 -(µ 4 -SCPhdCH)] prepared from [Os 4 (CO) 12 (µ 3 -S)] and HCtCPh, 20 and that in [Ru 4 (CO) 12 (µ 4 -SCdCCH 2 CMet Bu)] from [Ru 3 (CO) 12 ] and phenylthiocyclobutene PhSCd CHCH 2 C(Me) t Bu.…”

Structures and Reactivities of Palladium−Ruthenium Mixed-Metal Sulfido Clusters Derived from Disulfido- or Hydrosulfido-Bridged Diruthenium Complexes

“…It is well-recognized that palladium and ruthenium exhibit various catalytic activities in their own right, and extensive studies have been undertaken on the chemistry of palladium and ruthenium complexes. However, the palladium−ruthenium mixed-metal complexes are somehow surprisingly scarce even in the vast candidates included in the low-valent metal carbonyl category. − As an application of our cluster synthesis based on the bridging disulfido and hydrosulfido functionalities, we report here the syntheses of the palladium−ruthenium mixed-metal sulfido clusters [(Cp*Ru) 2 (μ 3 -S) 2 Pd 2 (μ 2 -SPr i )(SPr i )(PPh 3 )] ( 2 ) and [(Cp*Ru) 2 (μ 3 -S) 2 Pd 2 (μ 2 -Cl)(PPh 3 ) 2 ]Cl ( 7 ) from the diruthenium complexes 1 and 6 . Ligand substitution and core transformation reactions of these Pd 2 Ru 2 clusters are also described.…”

Synthesis and Reactivity of Hybrid Phosphido- and Hydrosulfido-Bridged Diruthenium Complexes: Transformations into Diruthenium and Tetraruthenium Complexes Bridged by Phosphido and Sulfido Ligands

“…The two ruthenium atoms also connect to each other by a Ru–Ru single bond at a distance of 2.7254(4) Å. The C(1)–C(2) bond length at 1.393(4) Å is intermediate between the typical C–C single- and double-bond distances and is comparable to those in the π-bonded alkenethiolato ligands of [Cp*Ir­{μSC­(Me)CHCH 2 COMe}] 2 [BF 4 ] 2 (1.392(9) Å) and [(Cp*Ru) 2 (CpTi) 2 Pd 2 (PPh 3 )­(μ 3 -S) 3 (μ 2 -O)­{μ 3 -SC­(COOMe)CCOOMe}] (1.401(9) Å), while the Ru(1)–C(1) and S(1)–C(2) distances at 2.023(4) and 1.772(3) Å, respectively, in 6 are comparable to those for Ru–C and S–C single bonds. The torsion angles of S(1)–Ru(1)–C(1)–C(2) (7.90(11)°) and Ru(1)–S(1)–C(2)–C(3) (−164.21(18)°) indicate that five atoms (Ru(1), C(1), C(2), C(3), and S(1)) are nearly coplanar.…”