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- W2054332203 abstract "Several [Co−Co]−alkyne adducts [Co2(CO)6)(μ-η2,η2-HOCR1R2-C⋮C−CR1R2OH)] were prepared (R1 = R2 = H (1); R1 = H, R2 = CH3 (2); R1 = R2 = CH3 (3)) and their X-ray molecular structures determined, showing that the μ-alkyne unit adopts a specific geometry depending on the nature of the alkyne unit. The prochiral [Mo−Co]−alkyne adduct [CpMoCo(CO)5(μ-η2,η2-HOCH2−C⋮C−CH2OH)] (4), identified by X-ray analysis, was obtained from [Co2(CO)6)(μ-η2,η2-HOCH2−C⋮C−CH2OH)] (1) via replacement of a −Co(CO)3 vertex by the isolobal moiety −CpMo(CO)2. Complex 4 reacts with aqueous HBF4 to produce the dicationic tetranuclear species [{CpMoCo(CO)5(μ-η2,η3-CH2−C⋮C−CH2-)}2O][BF4]2 (5), which reacts further with nucleophiles to give a new dicationic tetranuclear species [{CpMoCo(CO)5(μ-η2,η2-Nu1−CH2−C⋮C−CH2−)}2O][BF4]2 (Nu1 = pyridine (6), 3-picoline (7), triphenylphosphine (8)), where the nucleophile has been introduced to the carbenium center (−CH2+). Subsequent treatment of these dications in acidic medium produces the carbenium ions [CpMoCo(CO)5(μ-η2,η3-Nu1−CH2−C⋮C−CH2)][BF4]2 (Nu1 = pyridine (9), 3-picoline (10), triphenylphosphine (11)), which further react with nucleophile Nu2 to produce dications [CpMoCo(CO)5(μ-η2,η2-Nu1−CH2−C⋮C−CH2−Nu2)][BF4]2 {Nu1 = Nu2 = pyridine (13); Nu1 = pyridine, Nu2 = triphenylphosphine (14); Nu1 = Nu2 = triphenylphosphine (15); Nu1 = Nu2 = 3-picoline (16); Nu1 = pyridine = Nu2 = 3-picoline (17)). This synthetic approach is unprecedented because it allows the placement of the same or different types of nucleophiles in a stepwise fashion at the two terminal carbon atoms of the acetylenic complex, yielding, for instance, the chiral dicationic [Mo−Co] cluster [CpMoCo(CO)5(μ-η2,η2-C6H5N−CH2−C⋮C−CH2−NC6H4(CH3))][BF4]2 (17). The X-ray molecular structures of 13, 16, and 17 belonging to this family were determined, including the first chiral [Mo−Co] complex (17) possessing two different functional groups. Further, the structure shows that the coordinated functionalized alkyne can adopt a specific geometry, whereby the two positively functionalized groups are situated on the same side of the cluster unit, available to bind molecules of opposite charge." @default.
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- W2054332203 date "1998-05-01" @default.
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- W2054332203 title "A General Route to Prochiral and Chiral Dicationic Molybdenum−Cobalt Acetylenic Complexes: Synthesis, Structures, and Reactivity" @default.
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- W2054332203 doi "https://doi.org/10.1021/om971029n" @default.
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