Formation of Novel Trinuclear μ₃-s-cis-η²:η²-1,3-Diene Complexes of Ruthenium Having an Agostic Ru−H−C Interaction. Direct Evidence for Diene Activation in Cooperation with the Three Metal Centers

Abstract

Trinuclear pentahydride complex [(C5Me5)Ru]3(μ-H)3(μ3-H)2 (1) reacts with 1,3-butadiene or isoprene to form a 1,3-dimetalloallyl complex [(C5Me5)Ru]3(H)4(μ3-η3-C(Me)CHC(R)).

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

“…We have previously reported that 1 reacts with isoprene to afford the μ 3 -η 2 :η 2 - s - cis -isoprene complex 6 , which has an agostic Ru–H–C interaction at one terminal carbon atom (Chart ). Complex 6 was gradually converted into a μ 3 -η 3 -dimetalloallyl complex by subsequent C–H bond scission followed by the insertion of the olefinic moiety into a Ru–H bond. …”

“…24 The 13 C signals stemming from the butadiene ligand (δ 26.8 (C out , t, J C−H = 153 Hz) and 41.2 (C in , d, J C−H = 154 Hz)) were observed in a significantly higher magnetic field region upon μ-η 2 :η 2 coordination in comparison to those of uncomplexed 1,3-butadiene (δ 116.6 (C out ) and 137.2 (C in )), 25 and these chemical shifts are comparable to those of s-cis-butadiene complex 6 (δ 31.0 and 49.3). 21 Reaction of 4 with Alkynes. The reaction of 4 with another four-electron ligand, alkyne, was also investigated.…”

Activation of Organic Substrates on Multi-Metallic Sites of Transition Metal Polyhydride Clusters Having C5Me5 Groups as Auxiliary Ligands

“…[35] The reaction of 12 with isoprene proceeded in a similar manner at ambient temperature to form the corresponding µ 3 -dimetalloallyl complex 31 [Equation (16)]. (16) The molecular structure of 30 was proven by X-ray crystallography.…”

Activation of Linear Alkanes by a Hydrido Triruthenium Cluster and Associated Skeletal Rearrangements

“…20,33 Similar to¯3-ethylidyne-¯3-ethyne complex 10a, which was obtained by the reaction of 1 with two molecules of acetylene, 19e the hydrido ligands of 8d migrate around the triruthenium core at ambient temperature. Although the motion of the hydrido ligands of 10a only results in site-exchange of the acetylenic protons and Cp* ligands, such motion in 8d affords positional isomer 8d¤; though 8d possesses a hydrido ligand on the RuRu edge beneath the quaternary carbon atom on the propyne ligand, 8d¤ possesses a hydrido ligand on the RuRu edge beneath the methine carbon of the propyne ligand.…”

“…The equilibrium among¯3-vinylidene complex 4,¯3-(¦)-alkyne complex 5, and¯3-dimetalloallyl complex 6 showed that terminal alkenes and alkynes, conjugated dienes, and linear alkanes acted as chemically equivalent species in the reaction with 1; terminal alkenes, 20 terminal alkynes, 23 and conjugated dienes 33 reacted smoothly with 1 resulting in the quantitative formation of 4, 5, and 6, respectively. Such chemical equivalency among the hydrocarbons by the reaction with 1 shows potential utility of chemically inert alkanes for organotransformations.…”