UNUSUAL LIGAND FORMATION IN CS2 CHEMISTRY - SYNTHESIS, STRUCTURE, AND REACTIVITY OF MO2(S2CNET2)3(MU-CSC(S)S)(MU-S3C2NET2)
UNUSUAL LIGAND FORMATION IN CS2 CHEMISTRY - SYNTHESIS, STRUCTURE, AND REACTIVITY OF MO2(S2CNET2)3(MU-CSC(S)S)(MU-S3C2NET2)
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DOI：
10.1021/ic00217a049
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发表时间：
1985-01-01
影响因子：
4.6
通讯作者：
TEMPLETON, JL
中科院分区：
文献类型：
--
作者：
BURGMAYER, SJN;TEMPLETON, JL
CS_2与Mo（CO）_2（S_2CNEt_2）_2在2当量三苯基膦存在下发生配位反应，生成双核配合物Mo_2（S_2CNEt_2）_3（M-CSC（S）S）（^-S_3C_2NEt_2）（l）_，产率95%。通过单晶X射线衍射研究确定了1的身份。两个1分子的结晶空间群为PI，其中a= 15.749（6）A，B= 16.013（7）A，c= 9.740（6）A，a= 107.26（3），A = 105.92（4），和T = 71.14（2）。结构表明，一个分子的二硫化碳和两个硫代羰基单元已纳入两个新的配体。一个配体是CS与CS2偶联形成的-CSC（= S）S-单元，其中碳桥接两种金属，硫化物末端螯合一个钼。第二个配体似乎是通过硫代羰基插入二硫代氨基甲酸酯（S2 CNEt 2）的氘-硫键中形成的，得到-SC（SC（S）NEt 2）部分。硫代羰基-CS单元垂直桥接金属-金属轴，并使人联想到桥接炔。该配体还通过二硫代氨基甲酸盐硫螯合到一种金属。1与2（µ-8）（µ-= CEt）（S2 CNMe 2）3（SCNMe 2）（4）的结构相似，这促使我们从对双核炔衍生物4的分析中发展出1的定性分子轨道方案。这两种双核化合物都具有形式上的Mo（III）中心，其几何构型大致为conlateralbiocutahedral.使用[Me 30][BF 4]试剂添加Me+产生阳离子，其随后可以使用K [HB（0-i-Pr）3]还原。比较这些双核物质的循环伏安法和可见光谱数据。
The complex reaction of CS2 with Mo (CO) 2 (S2CNEt2) 2 in the presence of 2 equiv of triphenylphosphine forms the dinuclear complex Mo2 (S2CNEt2) 3 (M-CSC (S) S)(^-S3C2NEt2)(l) _in 95% yield. Theidentity of 1 was determined by a single-crystal X-ray study. Two molecules of 1 crystallize in space group PI with a= 15.749 (6) Á, b= 16.013 (7) A, c= 9.740 (6) Á, a= 107.26 (3), ß= 105.92 (4), and 7= 71.14 (2). The structure reveals that one molecule of carbon disulfide andtwo thiocarbonyl units havebeen incorporated in two new ligands. One ligand results from CS couplingwith CS2 to form a-CSC (= S) S-unit where the carbon bridges both metals and the sulfide terminus chelates to one molybdenum. The second ligand appears to form by thiocarbonyl insertion into a molybdenum-sulfide bond of a dithiocarbamate (S2CNEt2) to give a-SC (SC (S) NEt2) moiety. The thiocarbonyl-CS unit perpendicularly bridges the metal-metal axis and is reminiscent of a bridging alkyne. This ligand also chelates to one metal through a dithiocarbamate sulfur. The similarity of the structure of 1 to that of 2 (µ-8)(µ-= CEt)(S2CNMe2) 3 (SCNMe2)(4) encourages development of a qualitative molecular orbital scheme for 1 from the analysispresented for the dinuclear alkyne derivative 4. Both of these dinuclear compounds have formal Mo (III) centers in roughly conlateralbioctahedral geometries. Addition of Me+ using the [Me30][BF4] reagent yields a cation that may be subsequently reduced with use of K [HB (0-i-Pr) 3], Cyclic voltammetry and visible spectroscopy data are compared for these dinuclear species.