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• W2064545832 abstract "This paper describes the sequential assembly of up to three dithiolene ligands from alkynes and elemental sulfur at a dimetal center. The dimolybdenum μ-alkyne complexes [Mo2(μ-R1C≡CR2)(CO)4Cp2] (1a−c; Cp = η-C5H5, R1 = R2 = H, CO2Me; R1 = H, R2 = CO2Me) undergo oxidative decarbonylation on reaction with elemental sulfur in refluxing toluene to give good to excellent yields of the terminal dithiolene complexes [Mo2(S)(μ-S)2(SCR1═CR2S)Cp2] (2a−c). Further reaction of these complexes with 1 equiv of an alkyne R3C≡CR4 (R3 = R4 = H, CO2Me; R3 = H, R4 = CO2Me) followed by oxidation with elemental sulfur produces the bis(dithiolene) complexes [Mo2(μ-S)2(SCR1═CR2S)(SCR3═CR4S)Cp2] (4a−d). Two examples, [Mo2(μ-S)2(S2C2H2)2Cp2] and [Mo2(μ-S)2{S2C2(CO2Me)2}2Cp2], have been structurally characterized. Reaction of 2 with an excess of an activated alkyne R5C≡CR6 (R5 = R6 = CO2Me) and sulfur, or of 4 with the alkyne alone, affords good yields of the tris(dithiolene) complexes [Mo2(SCR1═CR2S)(SCR3═CR4S)(SCR5═CR6S)Cp2] (6a−e). The degree of control over the substituents in these complexes is demonstrated by the synthesis of [Mo2(S2C2H2){μ-S2C2(CO2Me)2}{μ-S2C2(CO2Et)2}Cp2] (6e), which contains three different dithiolene ligands, as a single isomer." @default.
• W2064545832 created "2016-06-24" @default.
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• W2064545832 date "2009-08-21" @default.
• W2064545832 modified "2023-10-18" @default.
• W2064545832 title "Sequential Construction of One, Two, or Three Dithiolene Ligands from Alkynes and Sulfur in Dinuclear Cyclopentadienyl Molybdenum Complexes" @default.
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• W2064545832 doi "https://doi.org/10.1021/ic901243m" @default.
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