Facile 1,2-Migration of a Methyl Group on a {Dimethoxy(methyl)silyl}tungsten Complex: Formation of a Base-Stabilized (Dimethoxysilylene)(methyl) Complex†
Facile 1,2-Migration of a Methyl Group on a {Dimethoxy(methyl)silyl}tungsten Complex: Formation of a Base-Stabilized (Dimethoxysilylene)(methyl) Complex†
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DOI：
10.1021/om100399s
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发表时间：
2010-07
期刊：
影响因子：
2.8
通讯作者：
E. Suzuki;Takashi Komuro;Yuto Kanno;M. Okazaki;H. Tobita
中科院分区：
文献类型：
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作者：
E. Suzuki;Takashi Komuro;Yuto Kanno;M. Okazaki;H. Tobita
Cp*（CO）2 W（DMAP）Me [1，Cp* = η5-C5 Me 5，DMAP = 4-（二甲氨基）吡啶]与三烷基硅烷HSiR 2 Et（R = Me，Et）反应，得到（DMAP）（三烷基硅基）钨配合物Cp*（CO）2 W（DMAP）（SiR 2 Et）（2a，R = Me; 2b，R = Et）。另一方面，1与二甲氧基（甲基）硅烷HSi（OMe）2 Me反应，通过甲基从硅向钨的1，2-迁移，得到DMAP稳定的（二甲氧基亚硅基）钨配合物cis-Cp*（CO）2 W（Me）{SiOSi（OMe）2·DMAP}（cis-3）。亚甲硅烷基络合物顺式-3异构化为其反式异构体反式-3。
Reactions of Cp*(CO)2W(DMAP)Me [1, Cp* = η5-C5Me5, DMAP = 4-(dimethylamino)pyridine] with trialkylsilanes HSiR2Et (R = Me, Et) afforded (DMAP)(trialkylsilyl)tungsten complexes Cp*(CO)2W(DMAP)(SiR2Et) (2a, R = Me; 2b, R = Et). On the other hand, a reaction of 1 with dimethoxy(methyl)silane, HSi(OMe)2Me, gave a DMAP-stabilized (dimethoxysilylene)tungsten complex, cis-Cp*(CO)2W(Me){═Si(OMe)2·DMAP} (cis-3), through 1,2-migration of a methyl group from silicon to tungsten. Silylene complex cis-3 isomerized to its trans-isomer trans-3.