Palladium-catalyzed selective dechlorination of polychloromethylsilanes with trichlorosilane
Palladium-catalyzed selective dechlorination of polychloromethylsilanes with trichlorosilane
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DOI：
10.1021/om970490c
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发表时间：
1998-02-16
期刊：
影响因子：
2.8
通讯作者：
Jung, IN
中科院分区：
文献类型：
--
作者：
Cho, YS;Han, JS;Jung, IN
研究了含氯甲基硅烷（Cl3-nCHn）SiCl3-mMem (n = 0-2 （1-3), m = 0-3 (a-d)）在10族过渡金属化合物存在下与三氯硅烷选择性脱氯的反应，反应温度为100 - 150℃。只有当Pd(OAc)(2)和PdCl2作为催化剂时，反应才能在不降低Si-Cl键的情况下得到相应的低氯化化合物。氯化甲基氯硅烷的脱氯速率取决于硅上的取代基和氯化碳上的氯原子数：随着碳上氯原子数和硅上甲基数的增加，脱氯速率也随之增加。（三氯甲基）-、（二氯甲基）-和（一氯甲基）氯硅烷的反应活性不同，可以通过控制三氯硅烷还原剂的用量和反应条件，从SiCC1(3)选择性地逐步还原为SiCHCl2、SiCH2Cl，最后还原为SiCH3。过渡金属化合物的催化活性依次降低：Pd(OAc)(2) > PdCl2远高于Pt-C、H2PtCl6、Ni(OAc)(2)、NiCl2 >、Pd(PPh3)(2)Cl-2、K2PtCl4。
Selective dechlorination of the chloromethyl-containing silanes (Cl3-nCHn)SiCl3-mMem (n = 0-2 (1-3), m = 0-3 (a-d)) with trichlorosilane was studied in the presence of group 10 transition-metal compounds at reaction temperatures between 100 and 150 degrees C in sealed bombs. The reactions give the corresponding less chlorinated compounds in good yields without reducing Si-Cl bonds, only when Pd(OAc)(2) and PdCl2 were used as catalysts. The dechlorination rate of chlorinated methylchlorosilanes depends on the substituents on silicon and the number of chlorine atoms on the chlorinated carbon: the rate increases as the number of chlorine atoms on carbon and of methyl groups on silicon increase. The reactivity difference between (trichloromethyl)-, (dichloromethyl)-, and (monochloromethyl)chlorosilanes allows selective stepwise reduction from SiCC1(3) to SiCHCl2 to SiCH2Cl and, finally, to SiCH3 by controlling the amount of trichlorosilane reductant and the reaction conditions. The catalytic reactivity of transition-metal compounds decreases in the following order: Pd(OAc)(2) > PdCl2 much greater than Pt-C, H2PtCl6, Ni(OAc)(2), NiCl2 > Pd(PPh3)(2)Cl-2, K2PtCl4.