Reactivity of triruthenium diphosphine clusters with 3,5-bis(trifluoromethyl)mercaptobenzene: Electronic and steric influence of diphosphines onto coordination modes of thiolate, capping sulfide, and phosphide groups to a Ru3 clusters

Treatment of the tetrahedral cluster H2Ru3(CO)9(μ3-S) (1) with 2-(diphenylphosphino)thioanisole (PS) furnishes the cluster H2Ru3(CO)7(κ2-PS)(μ3-S) (2). Cluster 2, which exhibits a chelated thiophosphine ligand (κ2-PS), exists as a pair of diastereomers with K eq = 1.55 at 298 K that differ in their disposition of ligands at the Ru(CO)(κ2-PS) center. The PS ligand occupies the equatorial sites (Peq,Seq) in the kinetic isomer and axial and equatorial sites (Pax,Seq) in the thermodynamically favored species. The solid-state structure of the kinetic isomer of 2 has been established by X-ray diffraction analysis, and the reversible first-order kinetics to equilibrium have been measured experimentally by NMR spectroscopy and HPLC over the temperature range 293–323 K. The substitution reaction involving 1 and the isomerization of the PS ligand in 2 were investigated by DFT calculations. The computational results support a phosphine-induced expansion of the cluster polyhedron that is triggered by the associative addition of the PS donor to 1. The vertex opening in 1 is selective and leads to the cleavage of a hydride-bridged Ru–Ru bond to give the phosphine-substituted cluster H2Ru3(CO)9(κ1-PS)(μ3-S) as the initial adduct. Chelation of the pendant MeS moiety follows with a loss of CO to give the kinetic substitution product H2Ru3(CO)7(κ2-Peq,Seq)(μ3-S) (2). The observed isomerization of the PS ligand in 2 is best explained by a tripodal rotation of the CO and PS groups at the Ru(CO)(κ2-PS) center that is preceded by a regiospecific migration of one of the edge-bridging hydrides to the nonhydride-bridged Ru–Ru bond in 2.

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Reactivity of triruthenium diphosphine clusters with 3,5-bis(trifluoromethyl)mercaptobenzene: Electronic and steric influence of diphosphines onto coordination modes of thiolate, capping sulfide, and phosphide groups to a Ru3 clusters

Cited by 3 publications

References 55 publications

Synthesis of the double spiked µ5-sulfide pentanuclear clusters using thermic reactions of Ru3-mercaptopyridine complexes

Synthesis of the double spiked µ5-sulfide pentanuclear clusters using thermic reactions of Ru3-mercaptopyridine complexes

Thermolysis of Ru3(CO)8(µ-dppm)(µ-dpam): Transformation of bis(diphenylphosphino)methane and bis(diphenylarsino)methane

Polyhedral Flexibility in the Sulfido-Capped Cluster H₂Ru₃(CO)₉(μ₃-S) on Reaction with 2-(Diphenylphosphino)thioanisole (PS) and Reversible Tripodal Rotation of the Chelated PS Ligand in H₂Ru₃(CO)₇(κ²-PS)(μ₃-S)

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Reactivity of triruthenium diphosphine clusters with 3,5-bis(trifluoromethyl)mercaptobenzene: Electronic and steric influence of diphosphines onto coordination modes of thiolate, capping sulfide, and phosphide groups to a Ru3 clusters

Cited by 3 publications

References 55 publications

Synthesis of the double spiked µ5-sulfide pentanuclear clusters using thermic reactions of Ru3-mercaptopyridine complexes

Synthesis of the double spiked µ5-sulfide pentanuclear clusters using thermic reactions of Ru3-mercaptopyridine complexes

Thermolysis of Ru3(CO)8(µ-dppm)(µ-dpam): Transformation of bis(diphenylphosphino)methane and bis(diphenylarsino)methane

Polyhedral Flexibility in the Sulfido-Capped Cluster H2Ru3(CO)9(μ3-S) on Reaction with 2-(Diphenylphosphino)thioanisole (PS) and Reversible Tripodal Rotation of the Chelated PS Ligand in H2Ru3(CO)7(κ2-PS)(μ3-S)

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Polyhedral Flexibility in the Sulfido-Capped Cluster H₂Ru₃(CO)₉(μ₃-S) on Reaction with 2-(Diphenylphosphino)thioanisole (PS) and Reversible Tripodal Rotation of the Chelated PS Ligand in H₂Ru₃(CO)₇(κ²-PS)(μ₃-S)