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• W2327443279 abstract "The alkynyl-bridged triruthenium cluster Ru3(CO)99μ2-H(μ3-ν2-CtBu) (1) reacts with the redox-active diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3,-dione (bpcd) in the presence of Me3NO to afford the new cluster Ru3(CO)7(μ2-H)(μ3-ν2-CCtBu)(bpcd) (2) in 76% yield. The diphosphine ligand in 2 is bound at the unique ruthenium atom in a chelating fashion, and is the first example of a cluster-coordinated bpcd ligand. Cluster 2 has been characterized in solution by IR and NMR (1H and 31P) spectroscopy and in the solid state by X-ray diffraction analysis. Ru3(CO)7(μ3-ν2-CCtBu)(bpcd), as the CH2Cl2 solvate, crystallizes in the monoclinic space group P21/c: α = 21.190(1), b = 12.345(1) Å, c = 17.272(1) Å, β = 95.075(5)°, V = 4500.5(5) Å,3, Z = 4, dcalc = 1.667 g cm−3; R = 0.399, Rw = 0.0432 for 3255 observed reflections. The redox properties of 2 were explored by cyclic voltammetry, which revealed the presence of a reversible one-electron reduction process (bpcd based) and an irreversible oxidation (metal based). The nature of the HOMO and LUMO in 2 has been examined by carrying out extended Hückel MO calculations on the model cluster Ru3(CO)7(μ2-H)(μ3-ν2-CCHH4-bpcd), and the results are discussed with respect to the observed electrochemistry. The propensity of cluster 2 to undergo P-C bond cleavage is discussed in the light of other diphosphine ligand work." @default.
• W2327443279 created "2016-06-24" @default.
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• W2327443279 date "1995-12-01" @default.
• W2327443279 modified "2023-09-26" @default.
• W2327443279 title "Ligand substitution of the redox-active diphosphine 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in the alkynyl-bridged cluster Ru3(CO)9(μ2-H)(μ3-ν2-CCtBu). Synthesis, X-ray structure and electrochemical properties of Ru3(CO)7(μ2-H)(μ3-ν2-CCtBu) (bpcd)" @default.
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• W2327443279 doi "https://doi.org/10.1016/0022-328x(95)05564-1" @default.
• W2327443279 hasPublicationYear "1995" @default.
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