Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai, 200 433, China.
Dalton Trans. 2011 Aug 14;40(30):7730-6. doi: 10.1039/c0dt01800g. Epub 2011 Mar 11.
Tridentate dianionic arylsulfide free ligands [ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh] (Ar = Ph (3a); Ar = 2,4,6-trimethylphenyl (3b); Ar = 2,6-diisopropylphenyl (3c)) have been prepared by reduction of the corresponding imine compounds [ArN[double bond, length as m-dash]CHC(6)H(4)NHC(6)H(4)-2-SPh] (Ar = Ph (2a); Ar = 2,4,6-trimethylphenyl (2b); Ar = 2,6-diisopropylphenyl (2c)) with LiAlH(4) in high yields. Reactions of TiCl(4) with the tridentate dianionic arylsulfide free ligands (3a-3c) afford five-coordinate and four-coordinate titanium complexes [κS, κ(2)N-(ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh)TiCl(2)] (Ar = Ph (4a); Ar = 2,4,6-trimethylphenyl (4b)] and [κ(2)N-(ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh)TiCl(2)] (Ar = 2,6-diisopropylphenyl (4c)], respectively. The molecular structures of compounds 2b, 2c, 3b and 3c·HCl have been characterized by single crystal X-ray diffraction analyses. Complexes 2a-4c are characterized by IR,(1)H-NMR spectra, and elemental analysis. EXAFS spectroscopy performed on complexes 4b and 4c reveals the expected different coordination geometry due to steric hindrance effect. When activated by excess methylaluminoxane (MAO), 4a-4c can be used as catalysts for ethylene polymerization and exhibit moderate to good activities.
三齿二价芳基硫醚自由配体[ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh]（Ar = Ph（3a）；Ar = 2,4,6-三甲基苯基（3b）；Ar = 2,6-二异丙基苯基（3c））是通过相应亚胺化合物[ArN[双键，长度为 m-dash]CHC(6)H(4)NHC(6)H(4)-2-SPh]（Ar = Ph（2a）；Ar = 2,4,6-三甲基苯基（2b）；Ar = 2,6-二异丙基苯基（2c））与 LiAlH(4)还原得到的，产率很高。TiCl(4)与三齿二价芳基硫醚自由配体（3a-3c）反应得到五配位和四配位钛配合物[κS，κ(2)N-(ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh)TiCl(2)]（Ar = Ph（4a）；Ar = 2,4,6-三甲基苯基（4b））和[κ(2)N-(ArNHCH(2)C(6)H(4)NHC(6)H(4)-2-SPh)TiCl(2)]（Ar = 2,6-二异丙基苯基（4c））。化合物 2b、2c、3b 和 3c·HCl 的分子结构通过单晶 X 射线衍射分析得到了表征。配合物 2a-4c 的特征在于 IR、(1)H-NMR 谱和元素分析。对配合物 4b 和 4c 进行的 EXAFS 光谱研究表明，由于空间位阻效应，预期会出现不同的配位几何形状。当用过量的甲基铝氧烷（MAO）激活时，4a-4c 可用作乙烯聚合的催化剂，并表现出中等至良好的活性。
