Reactions of HOSiMe2Ar with PtPPh3 complexes leading to Si-C bond activation or formation of a siloxoplatinum complex
Reactions of HOSiMe2Ar with PtPPh3 complexes leading to Si-C bond activation or formation of a siloxoplatinum complex
复制标题
DOI：
10.1016/s0022-328x(01)00796-3
复制
发表时间：
2001-06-01
影响因子：
2.3
通讯作者：
Osakada, K
中科院分区：
文献类型：
--
作者：
Mintcheva, N;Nishihara, Y;Osakada, K
在AgBF_4存在下，PtI_2（PPh_3）（2）与HOSiMe_2（C_6 H_4CF_3 -4）在60 ℃下反应，得到反式-PtI（C_6 H_4CF_3 -4）（PPh_3）（2）（1）和[Pt-2（mu -I）（2）（PPh_3）（4）]（BF_4）（2）（2）的混合物。每个复合物被分离并通过X射线晶体学和/或NMR光谱学表征。对AgBF 4与PtI 2（PPh 3）（2）在丙酮-d（6）中的反应进行的P-31{H-1}-NMR研究表明，形成了反式-[PtI（PPh 3）（2）（丙酮）] BF 4（3），尽管由于其容易转化为2，因此分离阳离子络合物是不可行的。将HOSiMe 2（C6 H4 CF 3 -4）和Ag 2 O加入到trans-PtI（Ph）（PPh 3）（2）的甲苯溶液中，导致碘代配体被取代，得到trans-[Pt（Ph）{OSiMe 2（C6 H4 CF 3 -4）}（PPh 3）（4）]（4）。4的晶体学结果显示苯基、邻位和PPh 3配体与具有大Pt-O-Si角的正方形平面Pt中心配位。配合物4在低于60 ℃的甲苯溶液中不分解，但在室温下与CH 2Cl 2和CHCl 3反应形成trans-Pt-Cl（Ph）（PPh 3）（2）（5）。(C)2001 Elsevier Science B. V.保留所有权利。
PtI2(PPh3)(2) reacts with HOSiMe2(C6H4CF3-4) at 60 degreesC in the presence of AgBF4 to give a mixture of trans-PtI(C6H4CF3-4)(PPh3)(2) (1) and [Pt-2(mu -I)(2)(PPh3)(4)](BF4)(2) (2). Each of the complexes is isolated and characterized by X-ray crystallography and/or NMR spectroscopy. The P-31{H-1}-NMR study of the reaction of AgBF4 with PtI2(PPh3)(2) in acetone-d(6) revealed the formation of trans-[PtI(PPh3)(2)(acetone)]BF4 (3) although isolation of the cationic complex was not feasible due to its facile conversion to 2. Addition of HOSiMe2(C6H4CF3-4) and Ag2O to a toluene Solution of trans-PtI(Ph)(PPh3)(2) causes replacement of the iodo ligand with the siloxo group to afford trans-[Pt(Ph) {OSiMe2(C6H4CF3-4)} (PPh3)(4)] (4). Crystallographic results of 4 show the coordination of the phenyl, siloxo, and PPh3 ligands to the square-planar Pt center with a large Pt-O-Si angle. Complex 4 does not decompose below 60 degreesC in a toluene solution, but reacts with CH2Cl2 and CHCl3 at room temperature to form trans-Pt-Cl(Ph)(PPh3)(2) (5). (C) 2001 Elsevier Science B.V. All rights reserved.