Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India.
Inorg Chem. 2010 Sep 6;49(17):7741-7. doi: 10.1021/ic100520k.
Reaction of [CpMoCl(4)], 1 (Cp = eta(5)-C(5)Me(5)), with [LiBH(4).thf] in toluene at -70 degrees C, followed by pyrolysis with excess dichalcogenides RE-ER (R = Ph, CH(2)Ph, 2,6-((t)Bu)(2)-C(6)H(2)OH, (CH(3))(3)C = (t)Bu); E = S, Se) yielded a new class of hybrid clusters, 3-8: (3, [(CpMo)(2)(mu-eta(1)-SPh)(2)(mu(3)-S)(H(2)BSPh)]; 4, [(CpMo)(2)B(5)H(8)(SPh)]; 5, [(CpMo)(2)B(5)H(8)(SePh)]; 6, [(CpMo)(2)B(2)S(2)H(2)(mu-eta(1)-S)]; 7, [(CpMo)(2)B(2)H(5)(BSR)(2)(mu-eta(1)-SR)], (R = 2,6-((t)Bu)(2)-C(6)H(2)OH); and 8, [(CpMo)(2)B(2)H(5)(BSePh)(2)(mu-eta(1)-SePh)]. Compounds 3-8 have been isolated in modest yields as green or brown crystalline solids. In parallel with 3-8, [(CpMo)(2)B(5)H(9)] was isolated as a major product in all cases. The isolation and structural characterization of compounds 3 and 6-8 provided the first direct evidence of the existence of [(CpMo)(2)B(4)H(8)], 2, an intermediate in the formation of [(Cp*Mo)(2)B(5)H(9)]. These new compounds have been characterized in solution by mass spectrometry, (1)H, (11)B, (13)C NMR, and IR spectroscopy, and elemental analysis. The structural types were unequivocally established by X-ray crystallographic analysis of compounds 3-8.
[CpMoCl(4)]（1，Cp=η(5)-C(5)Me(5)）与[LiBH(4).thf]在-70°C下的甲苯溶液反应，然后与过量的二卤代物RE-ER（R=Ph，CH(2)Ph，2,6-((t)Bu)(2)-C(6)H(2)OH，(CH(3))(3)C=(t)Bu；E=S，Se）进行热解，得到了一类新的混合簇，3-8：（3，[(CpMo)(2)(μ-η(1)-SPh)(2)(μ(3)-S)(H(2)BSPh)]；4，[(CpMo)(2)B(5)H(8)(SPh)]；5，[(CpMo)(2)B(5)H(8)(SePh)]；6，[(CpMo)(2)B(2)S(2)H(2)(μ-η(1)-S)]；7，[(CpMo)(2)B(2)H(5)(BSR)(2)(μ-η(1)-SR)]，（R=2,6-((t)Bu)(2)-C(6)H(2)OH）；和 8，[(CpMo)(2)B(2)H(5)(BSePh)(2)(μ-η(1)-SePh)]。这些化合物以中等产率作为绿色或棕色晶体固体分离出来。与 3-8 平行的是，在所有情况下都分离出主要产物[(CpMo)(2)B(5)H(9)]。化合物 3 和 6-8 的分离和结构表征提供了[(CpMo)(2)B(4)H(8)]（2）存在的直接证据，2 是[(Cp*Mo)(2)B(5)H(9)]形成过程中的中间产物。这些新化合物已通过质谱、(1)H、(11)B、(13)C NMR 和 IR 光谱以及元素分析在溶液中进行了表征。通过对化合物 3-8 的 X 射线晶体学分析，明确了结构类型。
