Transformation of a μ₃-Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ₃-Sulfido Ligand

Abstract

A triruthenium complex containing μ 3 -η 2 (||)-benzyne and μ 3 -sulfido ligands, [(Cp*Ru) 3 (μ 3 -S){μ 3 -η 2 (||)-C 6 H 4 }(μ-H)] (2), was synthesized by the reaction of [(Cp*Ru) 3 (μ 3 -S)(μ-H) 3 ] (1) with benzene. Although 2 was stable toward oxygen and water, two-electron oxidation of 2 with a Ag(I) salt in the presence of water afforded the dicationic μ-hydroxo complex [(Cp*Ru) 3 (μ 3 -S){μ 3η 2 (||)-C 6 H 4 }(μ-OH)] 2+ (3). Treatment of 3 with amine resulted in the deprotonation of the μ-hydroxo ligand, and an unsaturated monocationic complex, [(Cp*Ru) 3 (μ 3 -S)(μ 3 -OC 6 H 4 -κO,κC)] + (4), which possesses a μ 3 -cyclohexadienonediyl ligand, was formed via reductive C−O bond formation between the μ 3benzyne and transient μ-oxo ligands. Phenol was extruded from the Ru 3 cluster upon the hydrogenation of 4 via the formation of a μ 3 -phenoxo complex, [(Cp*Ru) 3 (μ 3 -S){μ 3 -OPh}(μ-H)] + (5). The cyclic voltammogram of 2 shows two reversible one-electron redox waves, and a dicationic μ 3 -benzyne complex, [(Cp*Ru) 3 (μ 3 -S){μ 3 -η 2 :η 2 (⊥)-C 6 H 4 }(μ-H)] 2+ (8), was shown to be responsible for the uptake of water to yield μ-hydroxo complex 3.

Phenylchromium(III) Chemistry Revisited 100 Years afterFranz Hein(Part III): From (Ar)3–nCrCln(L)x(Ar = Ph,p-F-C6H4, C6D5;n= 0, 1, 2; L = thf, dme, tmeda, 12C4) to Bis(π-arene)chromium Complexes

“…Despite the fact that dehydrobenzene is a highly reactive unstable compound under standard conditions, transition metal–organic compounds with this ligand are known to show three coordination modes: mononuclear η 2 -benzyne complexes (C–C: 132.0(6)–137.0(6) pm), dinuclear μ- o -phenylene complexes (C–C: 139–141 pm), and trinuclear μ 3 -η 2 -(C 6 H 4 ) 2– complexes that formed during heating of phenyl compounds with M 3 (CO) 12 (M = Os, Ru) . However, this type is also known for other transition-metal complexes (C–C: 140.0(7)–143.4 pm) …”

“…trinuclear μ 3 -η 2 -(C 6 H 4 ) 2– complexes that formed during heating of phenyl compounds with M 3 (CO) 12 (M = Os, Ru) . However, this type is also known for other transition-metal complexes (C–C: 140.0(7)–143.4 pm) …”

Study the Chemical Bonding of Heterometallic Trinuclear Cluster Containing Cobalt and Ruthenium: [(Cp*Co) (CpRu)2 (μ3-H) (μ-H)3] using QTAIM Approach

“…Due to their possible uses in catalytic or stoichiometric reactivity, there has been much investigation into the activation of transition metal clusters in the inorganic and organometallic chemistry disciplines due to their potential benefits in catalytic or stoichiometric reactivity 1 . Cluster complexes differ from mononuclear complexes in their reactivity in that they can coordinate with substrate molecules many times and mrof a multielectron transfer to the substrate 2,3 . Releasing bridging hydrido ligands from the polyhydrido cluster lerrdorprnlsuoeorsnops multiple unoccupied coordination sites on the neighboring metal centers 4-increased toward splitting inactive chemical bonds, such as the C−C and C−H bonds of alkanes 7 .…”

A Theoretical Investigation of Chemical Bonding of a Heterometallic Trinuclear Cluster Containing Iridium and Ruthenium: [(Cp*Ir) (CpRu)2 (μ3-H) (μ-H)3] by QTAIM Approach

“…Over the past years, several studies have been reported on the activation of transition metal clusters in inorganic and organometallic chemistry due to their possible uses in catalytic or stoichiometric reactivity 1,2 . These cluster complexes, which differ from mononuclear complexes in reactivity, can coordinate with substrate molecules many times and form a multi-electron transfer to the substrate 3,4 . In the polyhydrido clusters, the releasing of bridging hydrido ligands play an important spontaneously introducing multiple unoccupied coordination sites on the neighboring metal centers [5][6][7] .…”