Reactions of decaborane(14) with silylated acetylenes. Synthesis of the new monocarbon carborane 9-Me2S-7-[(Me3Si)2CH]CB10H11
Reactions of decaborane(14) with silylated acetylenes. Synthesis of the new monocarbon carborane 9-Me2S-7-[(Me3Si)2CH]CB10H11
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癸硼烷(14) 与甲硅烷基化乙炔的反应。
DOI：
10.1021/om00144a016
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发表时间：
1987
期刊：
影响因子：
--
通讯作者：
L. Sneddon
中科院分区：
文献类型：
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作者：
Robin L. Ernest;W. Quintana;R. Rosen;P. Carroll;L. Sneddon
已经研究了二甲基硫醚促进的十硼烷（14）与甲硅烷基化的乙炔、双（三甲基甲硅烷基）乙炔和（三甲基甲硅烷基）丙炔的反应，并且没有发现产生预期的oriho-carborane衍生物，而是产生烯基十硼烷或单碳硼烷产物。因此，在本发明中，癸硼烷（14）与二甲基硫醚和双（三甲基甲硅烷基）乙炔产生9-（CH 3）2S-7-[（（CH 3）3Si）2CH]-CB 10 H 11（I）和5-（CH 3）2S-6-[（（CH 3）3Si）2C= CH]-B 10 H 11（II），而与（三甲基硅烷基）丙炔生成5-（CH 3）2S-6-[（CH 3）3Si（CH 3）C= CH]-B10 Hn（III）。单晶X-射线衍射分析表明，化合物II和III是乙炔硼氢化反应的产物，其结构为癸硼烷（14）构型，其5-硼位上键合甲硫醚，6-硼位上键合烯基。III的晶体数据：空间群PI; Z= 4; a= 16.406（4）A，B= 16.677（5）A，c= 8.627（2）A，a= 100.67（2），λ = 97.78（2），λ = 118.23（2），V= 1974.9 A3;对于具有F02> 3（02）的5208个反射，R= 0.077和Pw= 0.103。化合物I的数据表明，它是一种不寻常的单碳碳硼烷，是由双（三甲基硅烷基）乙炔的乙炔碳中的一个插入笼状结构中而产生的。簇的几何形状是基于缺少一个顶点的二十面体，具有键合到笼状碳的外多面体双（三甲基甲硅烷基）甲基。研究了I与NaH、LiEt_3BH、Na或（7？5-C5 H6）2Co导致氢损失、二甲基硫醚解离和笼闭合以产生2-（（CH 3）3Si）2CH-CB 10 H10-阴离子。通过对茂钴盐VI的单晶X射线测定，确定该化合物具有基于十八面体的紧密结构，笼状碳占据结构中的四配位2-位。VI的晶体数据：空间群P21/rc; Z= 4; o= 12.260（1）A，B= 17.252（3）A，c= 13.701（3）A，λ = 107.94（1）; V= 2757.0 λ 3; R= 0.058和Rt = 0.068，对于具有F02> 3（02）的3061个反射。I在甲苯回流下的热分解得到主要产物6-（CH_3）_2S_2-[（（CH_3）_3Si）_2CH]-CB_10 H_9（VII），而I在固相中的热分解得到VII和少量的6-（CH_3）_2S_4-OH_2-[（（CH_3）_3Si）_2CH]-CB_10 H_8（VIII）。化合物VII和VIII与VI是等电子的，单晶X-射线测定证实VII和VIII具有相似的十八面体结构。VII的晶体数据：空间群PI; Z= 2;对于具有F2> 3（02）的2864个反射，a= 8.834（3）A，B= 19.211（2）A，c= 6.998（1）A，a= 96.20（1），λ = 109.63（2），λ = 91.91（2）; V= 1108.9 λ 3; R= 0.067和Pw= 0.081。VIII的晶体数据：空间群PI; Z= 4; a= 13.729（1）A，B= 16.345（2）A，c= 10.880（1）A，a= 96.62（1），λ = 93.45（1），λ = 74.47（1）; V= 2335.4 A3; R= 0.065和Pw= 0.078，对于具有F2> 3a（F2）的5623个反射。
The dimethyl sulfide promoted reactions of decaborane (14) with the silylated acetylenes, bis (tri-methylsilyl) acetylene and (trimethylsilyl) propyne, have been studied and were not found to yield the expected oriho-carborane derivatives but instead gave either alkenyldecaborane or monocarbon carborane products. Thus, the reaction of decaborane (14) with dimethyl sulfide and bis (trimethylsilyl) acetylene produced 9-(CH3) 2S-7-[((CH3) 3Si) 2CH]-CB1oH11 (I) and 5-(CH3) 2S-6-[((CH3) 3Si) 2C= CH]-B1oH11 (II) while the analogous reaction with (trimethylsilyl) propyne yielded5-(CH3) 2S-6-[(CH3) 3Si (CH3) C= CH]-B10Hn (III). A sin-gle-crystal X-ray determination of III demonstrated that compounds II and III result from acetylene hydroboration reactions andhave structures based on a decaborane (14) geometry with a dimethyl sulfide bound to the 5-boron and an alkenyl group bound to the 6-boron on the openface. Crystal data for III: space group PI; Z= 4; a= 16.406 (4) A, b= 16.677 (5) A, c= 8.627 (2) A, a= 100.67 (2), ß= 97.78 (2), 7= 118.23 (2), V= 1974.9 A3; R= 0.077 and Pw= 0.103 for the 5208 reflections having F02> 3 (02). The data obtained for compound I indicate that it is an unusual monocarbon carborane resulting from the insertion of only one of the acetyleniccarbons of the bis (trimethylsilyl) acetyleneinto the cage structure. The cluster geometry is based on an icosahedron missing one vertex, with an exopolyhedral bis (trimethylsilyl) methyl group bonded to the cage carbon. The reaction of I with either NaH, LiEt3BH, Na, or (7? 5-C5H6) 2Co results in hydrogen loss, dimethyl sulfide dissociation, and cage closure to yield the 2-((CH3) 3Si) 2CH-CB10H10~ anion. A single-crystal X-ray determination of the cobaltocenium salt VI established that the compound has a closo structure based on an octadecahedron, with the cage carbon occupying the four-coordinate 2-position in the structure. Crystal data for VI: space group P21/rc; Z= 4; o= 12.260 (1) A, b= 17.252 (3) A, c= 13.701 (3) A, ß= 107.94 (1); V= 2757.0 A3; R= 0.058 and R,,= 0.068 for the 3061 reflections having F02> 3 (02). Thermolysis of I at toluene reflux yielded as the major product 6-(CH3) 2S-2-[((CH3) 3Si) 2CH]-CB10H9 (VII) while thermolysis of I in the solid phase gave VII and small amounts of 6-(CH3) 2S-4-OH-2-[((CH3) 3Si) 2CH]-CB10H8 (VIII). Compounds VII and VIII are isoelectronic with VI, and single-crystal X-ray determinations confirmed that VII and VIII have similar octadecahedral structures. Crystal data for VII: space group PI; Z= 2; a= 8.834 (3) A, b= 19.211 (2) A, c= 6.998 (1) A, a= 96.20 (1), ß= 109.63 (2), 7= 91.91 (2); V= 1108.9 A3; R= 0.067 and Pw= 0.081 for the 2864 reflections having F2> 3 (02). Crystal data for VIII: space group PI; Z= 4; a= 13.729 (1) A, b= 16.345 (2) A, c= 10.880 (1) A, a= 96.62 (1), ß= 93.45 (1), 7= 74.47 (1); V= 2335.4 A3; R= 0.065 and Pw= 0.078 for the 5623 reflections having F, 2> 3a {F2).