Zhang Jia-Sheng, Lin Yue-Jian, Jin Guo-Xin
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai, 200433, China.
Dalton Trans. 2009 Jan 7(1):111-8. doi: 10.1039/b809520e. Epub 2008 Oct 30.
The 16-electron half-sandwich complexes CpM[S(2)C(2)(B(10)H(10))] (M = Ir (1), Rh (2), Co (3)) react with Ru(COD)Cl(2) under basic conditions at 35-40 degrees C to give different hetero-dinuclear clusters {CpM[S(2)C(2)(B(9)H(10))]}Ru(COD) (M = Ir (1a), Rh (2a), Co (3a)) and {CpM[S(2)C(2)(B(9)H(9))]}Ru(COD)(OCH(3)) (M = Ir (1b), Rh (2b), Co (3b)) with open carborane cages. Moreover, B-H-->Ru bridge bonds were observed in complexes 1a, 2a,3a . In reaction a, minor products trinuclear complex {CpIr[S(2)C(2)(B(10)H(10))]}(2)Ru (1c) and methoxyl-disubstituted complex CpIr[S(2)C(2)(B(10)H(8))(OCH(3))(2)] (1d) were successfully isolated. However, when the reaction temperature decreased to 0-10 degrees C, the kinetically-controlled products, mono-substituted complex CpIr[S(2)C(2)(B(10)H(9))(OCH(3))] (1e) and disubstituted complex CpIr[S(2)C(2)(B(10)H(8))(OCH(3))(2)] (1d), were isolated as the main products; nevertheless, the thermodynamically-controlled products, open-carborane complexes 1a and 1b , were isolated as the minor products. In complex CpCo[S(2)C(2)(B(9)H(10))]Ru(C(7)H(8)) (3c), one COD coordinated to ruthenium has been replaced by toluene. The reactions demonstrate that different types of products can be obtained by controlling the reaction conditions. All these new complexes have been characterized by IR, (1)H NMR, (11)B NMR and elemental analyses. The molecular structures of 1a, 1b, 1c, 1d, 1e, 2a and 3a have also been determined by single-crystal X-ray diffraction analyses.
16电子半夹心配合物CpM[S₂C₂(B₁₀H₁₀)]（M = Ir (1)、Rh (2)、Co (3)）在35 - 40℃的碱性条件下与[Ru(COD)Cl₂]ₓ反应，生成具有开放碳硼烷笼的不同异双核簇{CpM[S₂C₂(B₉H₁₀)]}Ru(COD)（M = Ir (1a)、Rh (2a)、Co (3a)）和{CpM[S₂C₂(B₉H₉)]}Ru(COD)(OCH₃)（M = Ir (1b)、Rh (2b)、Co (3b)）。此外，在配合物1a、2a、3a中观察到了B - H→Ru桥键。在反应a中，成功分离出了次要产物三核配合物{CpIr[S₂C₂(B₁₀H₁₀)]}₂Ru (1c)和甲氧基二取代配合物CpIr[S₂C₂(B₁₀H₈)(OCH₃)₂] (1d)。然而，当反应温度降至0 - 10℃时，动力学控制产物单取代配合物CpIr[S₂C₂(B₁₀H₉)(OCH₃)] (1e)和二取代配合物CpIr[S₂C₂(B₁₀H₈)(OCH₃)₂] (1d)被分离为主产物；不过，热力学控制产物开放碳硼烷配合物1a和1b被分离为次要产物。在配合物CpCo[S₂C₂(B₉H₁₀)]Ru(C₇H₈) (3c)中，一个与钌配位的COD已被甲苯取代。这些反应表明，通过控制反应条件可以获得不同类型的产物。所有这些新配合物均通过红外光谱、¹H核磁共振、¹¹B核磁共振和元素分析进行了表征。1a、1b、1c、1d、1e、2a和3a的分子结构也通过单晶X射线衍射分析确定。
