Reactions of Silanone(silyl)tungsten and -molybdenum Complexes with MesCNO, (Me2SiO)3, MeOH, and H2O: Experimental and Theoretical Studies
Reactions of Silanone(silyl)tungsten and -molybdenum Complexes with MesCNO, (Me2SiO)3, MeOH, and H2O: Experimental and Theoretical Studies
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硅酮（甲硅烷基）钨和硅酮配合物与 MesCNO、(Me2SiO)3、MeOH 和 H2O 的反应：实验和理论研究
DOI：
10.1021/acs.organomet.6b00958
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发表时间：
2017
期刊：
影响因子：
2.8
通讯作者：
and Keiji Ueno
中科院分区：
文献类型：
--
作者：
Takako Muraoka;Haruhiko Kimura;Gama Trigagema;Masayuki Nakagaki;Shigeyoshi Sakaki;and Keiji Ueno
研究了硅酮(硅基)钨钼配合物Cp*(OC)2M{OSiMes2(DMAP)}(SiMe3)(M=W(1a)，Mo(1b)，Cp*=η5-C5Me5，Mes=2，4，6-Me3C6H2，DMAP=4-(Me2N)C5H4N)与MeCNO、(Me2SiO)3、MeOH和H2O的反应。在1与MesCNO和(Me2SiO)3反应中没有检测到硅酮捕获产物，而1与甲醇反应生成了加成产物Mes2Si(OMe)OH(5)。钼络合物的水解产物以硅二醇Mes_2Si(OH)_2(8)为主，还有少量的Mes_2Si(OH)OSiMe_3(9)，而钨的类似物硅氧硅醇9则是唯一的产物，表明在水解过程中产物的分布明显依赖于金属碎片。理论研究表明，钨钼络合物的产物分布差异是由于硅酮配体中硅原子的亲电性不同，以及不能在Mii-L片段上氧化加成水所致。
Reactions of silanone(silyl)tungsten and -molybdenum complexes Cp*(OC)2M{OSiMes2(DMAP)}(SiMe3) (M = W (1a), Mo (1b), Cp* = η5-C5Me5, Mes = 2,4,6-Me3C6H2, DMAP = 4-(Me2N)C5H4N) with MesCNO, (Me2SiO)3, MeOH, and H2O were investigated. No silanone trapping product was detected in the reaction of1with MesCNO and (Me2SiO)3, while reactions of1with MeOH afforded the addition product Mes2Si(OMe)OH (5). The hydrolysis of molybdenum complex1bafforded silanediol Mes2Si(OH)2(8) as a main product with a trace amount of Mes2Si(OH)OSiMe3(9), while that of the tungsten analogue1agave siloxysilanol9as the sole product, indicating that product distribution in the hydrolysis strikingly depends on the metal fragments. A theoretical investigation revealed that the product distribution difference between tungsten and molybdenum complexes arises from the difference in electrophilicity of the silicon atom in the silanone ligand and that of the lability for oxidative addition of water to the MII–L fragment.