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- W1972009780 abstract "The reagent Li[7-NHBu(t)()-nido-7-CB(10)H(12)] reacts with [Mo(CO)(6)] in NCMe at reflux temperatures, followed by addition of [N(PPh(3))(2)]Cl, to give [N(PPh(3))(2)][1,2-mu-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-MoCB(10)H(10)] (1). The tungsten (2) and chromium (3) analogues were similarly obtained, but the latter is unstable and was isolated in low yield. An X-ray diffraction study of 2 confirmed that the exo-polyhedral NHBu(t) group forms a bridge between the cage-carbon atom and the tungsten. For 1, this intramolecular donor bond is lifted on protonation in the presence of donor molecules L (CO, PPh(3), PMe(3), PEt(3), PMe(2)Ph) when zwitterionic complexes [1-NH(2)Bu(t)()-2,2,2-(CO)(3)-2-L-closo-2,1-MoCB(10)H(10)] (4) are formed. In contrast, protonation with HCl gives a salt [N(PPh(3))(2)][1-NH(2)Bu(t)()-2,2,2-(CO)(3)-2-Cl-closo-2,1-MoCB(10)H(10)] (5). Complex 1 in CH(2)Cl(2) with CNBu(t) is oxidized by iodine, affording [1,2-mu-NHBu(t)()-2,2,2-(CNBu(t)())(3)-2-I-closo-2,1-MoCB(10)H(10)] (6a). Treatment of 1 with [CuCl(PPh(3))](4) in the presence of Tl[PF(6)] yields the bimetallic compound [exo-[Cu(PPh(3))]-1,2-mu-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-MoCB(10)H(10)] (8), whereas reaction with [AuCl(PPh(3))] and Tl[PF(6)] affords a mixture of [1,2-mu-NHBu(t)-2-[Au(PPh(3))]-2,2,2-(CO)(3)-closo-2,1-MoCB(10)H(10)] (9) and [Au(PPh(3))(2)][2,2'-mu-Au-[1,2-mu-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-MoCB(1)(0)H(10)](2)] (10a). In solution, 9 disproportionates, giving 10a. The [N(PPh(3))(2)](+) salt (10b) is readily prepared by treating 1 with [AuCl(THT)] (THT = tetrahydrothiophene) and Tl[PF(6)], and its structure was determined by X-ray diffraction." @default.
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- W1972009780 date "2001-11-08" @default.
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- W1972009780 title "Synthesis and Reactivity of the Monocarbon Molybdenacarborane Anion [1,2-<i>μ</i>-NHBu<i><sup>t</sup></i>-2,2,2-(CO)<sub>3</sub>-c<i>loso</i>-2,1-MoCB<sub>10</sub>H<sub>10</sub>]<sup>-</sup>" @default.
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- W1972009780 doi "https://doi.org/10.1021/ic010508i" @default.
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