16电子半夹心结构含硫碳硼烷钴配合物CptCoS2C2B10H10的合成以及结构表征

八羰基二钴Co2(CO)8与叔丁基取代的环戊二烯反应，可以得到半夹心结构的羰基钴化合物Cp^tCo(CO)2(2)(Cp^t=η^5-^tBuC5H4)，化合物(2)与元素碘进行反应可以被氧化成相应的钴的碘化产物Cp^tCo(CO)I2(3)，采用碳硼烷含硫锂化合物[(THF)3LiS2C2B10H10Li(THF)]2(1)与18电子半夹心结构羰基钴的碘化物Cp^tCo(CO)I2(3)反应得到16电子半夹心结构化合物Cp^tCoS2C2B10H10(4)，表征了化合物(2)，(3)和(4)，并解析了配合物(4)的X—衍射的单晶结构。     

含硫族元素碳硼烷半夹芯式有机金属钌化合物的研究进展

近年来邻位－碳硼烷及其衍生物的合成及应用研究是有机金属化学研究的热点。本文对含硫族元素碳硼烷半夹芯式有机金属钌化合物在设计、合成及相关方面的研究现状作了简要综述。     

浅议carborane及几个碳杂硼簇化合物的中文定名

根据基本定义和专门的命名规则,建议统一carborane 的中文定名为“碳硼烷”,C₂B₁₀H₁₂ 和C₂B₅H₇分别命名为“二碳代-闭式-十二硼烷”(其异构体为“邻-、间-、对碳硼烷”)和“二碳代-闭式-庚硼烷”。     

Synthesis and reaction of 16-electron Cp<Superscript>t</Superscript>Rh halfsandwich complexes containing 1,2-dichalcogenolate carborane ligands

The reactions of [Cp^tRhCi(μ-Ci)]2 (1) (Cp^t=^tBu2C5H3) with Li2E2C2B10H10 (E = S, Se) lead to the green 16-electron dichaicogenolate complexes Cp^tRh(E2C2B10H10) [E = S(2a), Se(2b)]. The 16-electron complexes 2a and 2b can take up two-electron donor ligands such as tert-butyi isonitrile and carbon monoxide to give the 18-electron dichaicogenolate derivatives Cp^t(L)(E2C2B10H10) [L = ^tBuNC, E =S(3a), Se(3b); L = CO, E = S(4a), Se(4b)]. The molecular structures of complexes 2a and 3a were determined by X-ray crystal structure analysis. The molecular structure of 16-electron complex 2a shows the pseudoaromatic system in IrSe2C2 five numbered ring.     

半夹芯16e化合物CpCoS2C2B10H10与FcC（O）C≡CH反应得到不含钴的产物：同时含有一个FcC（O）-CH=CH单元和一个双环[2．2．1]庚烯单元

半夹芯16e化合物CpCoS2C2810H10（1）与FeC（O）C≡CH反应得到两个不合钴的产物2-3。2-3含有一个与硫原子相连的VeC（O）-CH=CH单元和一个与碳硼烷笼体B（3）／B（6）位及另外一个硫原子同时相连的双环[2．2．1]庚烯单元。2-3用红外，核磁，元素分析，质谱和单晶X-射线衍射分析进行了结构表征。     

Structure and second-order NLO property of the molecules bridged through n-vertex bis-substituted carborane （n=5, 6, 7）

Density functional theory (DFT) B3LYP at 6-31G* level is employed to optimize the structures of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) and combined with finite field (FF) formalism to calculate the second-order NLO properties. The results indicate that the structures of n-vertex bis-substituted carborane (n=5, 6, 7) are changed due to bridged donor and acceptor moieties. The distances between two C atoms are becoming longer. And the stability and dipole moment are in- fluenced by changing substituted positions of C atoms. The isomers with the substituents connecting with C atoms of lower coordination number have better stability and larger values of polarizability. One-dimensional structure of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) is in favor of intramolecular charge-transfer. Meanwhile, the isomer with a larger change of dipole moment has larger value of second-order NLO properties during the charge-transfer process.     

半夹芯16电子碳硼烷有机金属化合物的反应性研究进展

邻位碳硼烷o-C2B10H12中CH单元上的H原子具有一定的弱酸性,可以和强碱n-BuLi反应,生成含有金属离子的盐,该盐再与硫族元素发生插入反应,形成锂盐Li2E2C2B10H10(E=S,Se),据此可以生成半夹芯16e碳硼烷有机金属化合物。这些半夹芯16e碳硼烷有机金属化合物金属中心电子的不饱和性,两个M-E键具有一定的化学活性,以及碳硼烷笼子中的B(3)/B(6)位的B-H键能够被活化,可以控制在不同的反应条件下与一系列供电子配体发生反应,生成许多结构新颖的产物。本文综述了半夹芯16e碳硼烷有机金属化合物的反应性研究进展。