Wang Xin, Jin Guo-Xin
Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, PR China.
Chemistry. 2005 Sep 19;11(19):5758-64. doi: 10.1002/chem.200500280.
The synthesis of half-sandwich transition-metal complexes containing the Cab(N) and Cab(N,S) chelate ligands (HCab(N) = HC2B10H10CH2C5H4N (1), LiCab(N,S) = LiSC2B10H10CH2C5H4N (4)) is described. Compounds 1 and 4 were treated with chloride-bridged dimers [{Ir(Cp*)Cl2}2] (Cp* = eta5-C5Me5), [{Ru(p-cymene)Cl2}2] and [{Rh(Cp*)Cl2}2] to give half-sandwich complexes [Ir(Cp*)Cl(Cab(N))] (2), [Ru(p-cymene)Cl(Cab(N))] (3), and [Rh(Cp*)Cl(Cab(N,S))] (5), respectively. Addition reaction of LiCab(S) (Cab(S) = SC2(H)B10H10) to the rhodium complex 5 yields [Rh(Cp*)(Cab(S))(Cab(N,S))] (6). All the complexes were characterized by IR and NMR spectroscopy, and by elemental analysis. In addition, X-ray structure analyses were performed on complexes 2, 3, 5, and 6, in which the potential C,N- and N,S-chelate ligands were found to coordinate in a bidentate mode. The carborane complex 2 shows catalytic activities up to 3.7x10(5) g PE mol(-1) Ir h(-1) for the polymerization of ethylene in the presence of methylaluminoxane (MAO) as cocatalyst. The polymer obtained from this homogeneous catalytic reaction has a spherical morphology. Catalytic activities and the molecular weight of polyethylene have been investigated for various reaction conditions.
本文描述了含Cab(N)和Cab(N,S)螯合配体（HCab(N) = HC2B10H10CH2C5H4N (1)，LiCab(N,S) = LiSC2B10H10CH2C5H4N (4)）的半夹心过渡金属配合物的合成。化合物1和4分别与氯桥联二聚体[{Ir(Cp*)Cl2}2]（Cp* = η5-C5Me5）、[{Ru(p-cymene)Cl2}2]和[{Rh(Cp*)Cl2}2]反应，分别得到半夹心配合物[Ir(Cp*)Cl(Cab(N))] (2)、[Ru(p-cymene)Cl(Cab(N))] (3)和[Rh(Cp*)Cl(Cab(N,S))] (5)。LiCab(S)（Cab(S) = SC2(H)B10H10）与铑配合物5发生加成反应生成[Rh(Cp*)(Cab(S))(Cab(N,S))] (6)。所有配合物均通过红外光谱、核磁共振光谱和元素分析进行了表征。此外，还对配合物2、3、5和6进行了X射线结构分析，发现潜在的C,N-和N,S-螯合配体以双齿模式配位。在甲基铝氧烷（MAO）作为助催化剂存在下，碳硼烷配合物2对乙烯聚合显示出高达3.7×10(5) g PE mol(-1) Ir h(-1)的催化活性。从该均相催化反应得到的聚合物具有球形形态。研究了各种反应条件下聚乙烯的催化活性和分子量。
