Stereochemistry of polynuclear compounds of the main group elements. XI. Dimethyl(methylthiol)aluminum, [(CH3)2AlSCH3]n, a new type of stereochemistry for an organoaluminum compound
Stereochemistry of polynuclear compounds of the main group elements. XI. Dimethyl(methylthiol)aluminum, [(CH3)2AlSCH3]n, a new type of stereochemistry for an organoaluminum compound
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主族元素多核化合物的立体化学。
DOI：
10.1021/ja01048a011
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发表时间：
1969
影响因子：
15
通讯作者：
G. Stucky
中科院分区：
文献类型：
--
作者：
D. Brauer;G. Stucky
用计数器法测定了二甲基甲硫基铝[（CH_3）_2Al_（SCH_3）]_n的三维X射线数据，确定了其晶体结构。[（CH 3）2A 1 SCH 3] n晶体属于正交晶系空间群Fdd 2，晶胞尺寸a= 25.679（7）A，B= 7.942（2）A，c= 12.004（3）A.每晶胞16个（CH 3）2AlSCH 3单元的计算密度为1.13 g cm-3，与观察到的密度1.14±0.03 g cm-8相当。三维最小二乘精化给出了445个反射的3.9%的常规加权R因子。在固态下，[（CH 3）2AlSCH 3] n是一个一维的无限聚合物，其甲基硫醇基团桥接二甲基铝基团，形成锯齿形的无限链。桥连硫原子呈锥形构型。Al-S平均键长为2.348（2）埃，Al-C平均键长为1.944（7）埃，CS平均键长为1.806（7）埃。Al-S-Al'角为103.0（1），S-Al-S'角为100.1（1）.烷基、卤素、3个仲胺、仲膦、4个仲胂、5和醇4 '6与三甲基铝形成有限多核化合物.当大的、庞大的基团与铝原子配位时，单体物质可以像在三异丁基铝中那样稳定。6较小的空间要求导致二聚化合物，
The crystal structure of dimethyl (methylthiol) aluminum,[(CH3) 2A1SCH3]„, has been determined from three-dimensional X-ray data measured by counter methods.[(CH3) 2A1SCH3]„crystallizes in the orthorhombic space group Fdd2 with cell dimensions a= 25.679 (7) A, b= 7.942 (2) A, and c= 12.004 (3) A. The calculated density of 1.13 g cm-3 for 16 (CH3) 2A1SCH3 units per unit cell compares well with the observed density of 1.14±0.03 g cm-8. Three-dimensional least-squares refinement gave a conventional weighted R factor of 3.9% for 445 reflections. In the solid state,[(CH3) 2AlSCH3] n is a one-dimensional infinite polymer with methylthiol groups bridging dimethylaluminum groupsto form zigzag infinite chains. The bridging sulfur atoms are in a pyramidal configuration. Theaverage Al-S bond length is 2.348 (2) A, the average Al-C bond distance is 1.944 (7) A, and the CS bond length is 1.806 (7) Á. The Al-S-Al'angle is 103.0 (1), and the S-Al-S'angle is 100.1 (1).It is well known that alkyls, halogens, 3 secondary amines, secondary phosphines, 4 secondary arsines, 5 and alcohols4’6 form finitepolynuclear compounds with trimethylaluminum. When large, bulky groups are co-ordinated to the aluminum atom, monomeric species can be stabilized as in triisobutylaluminum. 6 Some-what smaller steric requirements result in dimeric com-