Synthesis and characterization of heterometallic Rh/Ru complexes supported by 1,2-dichalcogenolato-o-carborane ligands

被引：19
作者：
Zhang, Jia-Sheng [1 ]
Lin, Yue-Jian [1 ]
Jin, Guo-Xin [1 ]
机构：
[1] Fudan Univ, Dept Chem, Shanghai Key Lab Mol Catalysis & Innovat Mat, Shanghai 200433, Peoples R China
来源：
JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2009年 / 694卷 / 13期
基金：
美国国家科学基金会;
关键词：
Heterometallic complex; Carborane; Molecular structure; Metal-metal bond; HALF-SANDWICH COMPLEXES; TRANSITION-METAL-COMPLEXES; B-H ACTIVATION; CP-ASTERISK-RH; CRYSTAL-STRUCTURES; 1,2-DICARBA-CLOSO-DODECABORANE-1,2-DITHIOLATE LIGAND; DERIVATIVES; RU; CO; REACTIVITY;
D O I：
10.1016/j.jorganchem.2009.02.009
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The 16-electron half-sandwich complexes Cp*Rh[E2C2(B10H10)] (E = S, 1a; Se, 1b) react with [Ru(COD)Cl-2](x) under different conditions to give different types of heterometallic complexes. When the reactions were carried out in THF for 24 h, the binuclear Rh/Ru complexes [Cp*Rh(mu-Cl)(2)(COD) Ru][E2C2(B10H10)] (E = S, 2a; Se, 2b) bridged by two Cl atoms and the binuclear Rh/Rh complexes (Cp*Rh)(2)[E2C2(B10H10)] (E = S, 3a; Se, 3b) with direct Rh-Rh bond can be isolated in moderate yields. [Ru(COD)Cl-2] fragments in 2a and 2b have inserted into the Rh-E bond. If the [Ru(COD) Cl2] x was reacted with 1a in the presence of K2CO3 in methanol solution, the product [Cp*Rh(COD)]Ru[S2C2(B10H10]] (4a), K[(mu-Cl)(mu-OCH3) Ru(COD)](4) (5a) and 3a were obtained. The B(3)-H activation in complex 4a was found. However, when the reaction between 1b and [Ru(COD)Cl-2](x) was carried out in excessive NaHCO3, the carborane cage opened products {Cp*Rh[S2C2(B9H10)]}Ru(COD) (6b), {Cp*Rh[S2C2(B9H9)]}Ru(COD)(OCH3) (7b) and 3b were obtained. All complexes were fully characterized by their IR, H-1 NMR and elemental analyses. The molecular structures of 2a, 2b, 3b, 4a, 5a, and 7b have been determined by X-ray crystallography. (c) 2009 Elsevier B.V. All rights reserved.
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页码：2069 / 2074
页数：6
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