| Abstrakt: |
Protonation of the 11-vertex bis-molybdenum−monocarbollide salt [NEt4]3[1,3,6-{Mo(CO)3}-3,6-(μ-H)2-1,1,1-(CO)3-2-Ph-closo-1,2-MoCB9H7] (1) with H[Mi4]·OEt2 in the presence of CO and [NEt4]I results in molybdenum oxidation and cage expansion to yield 12-vertex [NEt4][2,2,2-(CO)3-8-OH-2-I-1-Ph-closo-2,1,8-MoC2B9H9] (5). In contrast, oxidation of 1 with Ag[Mi4] in the presence of CNBut similarly results in metal oxidation but also in cage substitution to give 11-vertex [1,1,1,1,3-(CNBut)5-2-Ph-closo-1,2-MoCB9H8] (6). The latter is oxidized in air to afford an icosahedral, cage expansion species [8-NHBut-2,2-(CNBut)2-2-(&dbd;O)-1-Ph-closo-2,1,8-MoC2B9H9] (7). Oxidation of 1 with PhSSPh results in retention of both molybdenum atoms to give the bis-thiolato-bridged complex [1-{Mo(μ-SPh)2(CO)4}-2-Ph-closo-1,2-MoCB9H9]-, isolated as its [N(PPh3)2]+ salt (8). |
