Synthesis and Structural Characterization of New Rhodium-Tin Heterodimetallic Complexes
Synthesis and Structural Characterization of New Rhodium-Tin Heterodimetallic Complexes
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新型铑锡异二金属配合物的合成及结构表征
DOI：
10.1002/ejic.200701240
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发表时间：
2008
影响因子：
2.3
通讯作者：
L. Gade
中科院分区：
文献类型：
--
作者：
M. Kilian;H. Wadepohl;L. Gade
三氨基丁酸盐（II） MeSi{SiMe2N(p-tol)}3SnLi(OEt2) （1a）和MeSi{SiMe2N（3,5-羟基）}3SnLi(OEt2) （1b）与1/2摩尔等量的[RhCl（二烯烃）]2（二烯烃= COD， NBD）与磷、亚磷酸盐或异硝基(L)反应得到方形平面配合物[MeSi{SiMe2NAryl}3SnRh(L)（二烯烃）]（芳基= 3,5-羟基，p-tol），其中锡酸盐通过Rh-Sn键直接与铑成键。与此相反，以1/2等量的[RhCl(C2H4)2]和PiPr3在甲苯中的类似转化，得到的不是方形平面的二乙烯配合物[MeSi{SiMe2N（3,5-羟基）}3SnRh(C2H4)2(PiPr3)]，而是棕色的18e π-芳烃配合物[MeSi{SiMe2N（3,5-羟基）}3SnRh(PiPr3)（η - 6-甲苯）](6)。用π-芳烃体系（如6）对方形平面二烯烃配合物在甲苯中溶解时进行了平衡。（©Wiley-VCH Verlag GmbH & Co. KGaA，德国Weinheim 69451, 2008）
Reaction of the triamidostannates(II) MeSi{SiMe2N(p-tol)}3SnLi(OEt2) (1a) and MeSi{SiMe2N(3,5-xyl)}3SnLi(OEt2) (1b) with 1/2 molar equiv. of [RhCl(diolefin)]2 (diolefin = COD, NBD) and phosphanes, phosphites or isonitriles (“L”) gave the square-planar complexes [MeSi{SiMe2NAryl}3SnRh(L)(diolefin)] (Aryl = 3,5-xyl, p-tol) in which thestannates are directly bonded to rhodium through Rh–Sn bonds. In contrast, the analogous transformation of 1b with 1/2 equiv. of [RhCl(C2H4)2]2 and PiPr3 in toluene did not lead to a square-planar bisethylene complex [MeSi{SiMe2N(3,5-xyl)}3SnRh(C2H4)2(PiPr3)] but the brown 18e π-arene complex [MeSi{SiMe2N(3,5-xyl)}3SnRh(PiPr3)(η6-toluene)] (6). Equilibria of the square planar diolefin complexes with π-arene systems such as 6 were observed upon their dissolution in toluene.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)