Unexpected carbon-oxygen bond cleavage of THF promoted by guanidinate titanium complex/lithium diisopropylamide: Synthesis and crystal structure  

作　　者：ZHANG Yong WANG Mei YAO Yingming SHEN Qi 

机构地区：[1]Key Laboratory of Organic Synthesis, Department of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215006, China [2]Department of Public Course, Bengbu Medical College,Bengbu 233003, China

出　　处：《Chinese Science Bulletin》2005年第24期2817-2820,共4页

基　　金：supported by the National Natural Science Foundation of China(Grant No.20472063).

摘　　要：An unexpected carbon-oxygen bond cleavage of THF (THF = tetrahydrofuran) promoted by guanidinate titanium complex was described. Guanidinate lithium [Pr2iNC(NCy)2]Li (Cy = cyclohexyl) formed in situ reacted with TiCl4(THF)2 in a 2:1 molar ratio to produce the gua- nidinate titanium chloride [Pr2iNC(NCy)2]2TiCl2 (1) in good yield. The reaction of [Pr2iNC(NCy)2]2TiCl2 with lithium diisopropylamide in THF afforded an unexpected [Pr2iNC(NCy)2]2Ti(OBun)2 (2), which was formed by the cleavage of carbon-oxygen bond of THF. Complexes 1 and 2 were fully characterized by elemental analysis, NMR and IR spectroscopies, and X-ray crystal structure determination for complex 2.An unexpected carbon-oxygen bond cleavage of THF （THF = tetrahydrofuran） promoted by guanidinate titanium complex was described. Guanidinate lithium [Pr2 ^1NC（NCy）2]Li （Cy = cyclohexyl） formed in situ reacted with TiCl4（THF）2 in a 2：1 molar ratio to produce the guanidinate titanium chloride [Pr2 ^1NC（NCy）2]2TiCl2 （1） in good yield. The reaction of [Pr2 ^1NC（NCy）2]2TiCl2 with lithium diisopropylamide in THF afforded an unexpected [Pr2 ^1NC（NCy）2]2Ti（OBu^n）2 （2）, which was formed by the cleavage of carbon-oxygen bond of THF. Complexes 1 and 2 were fully characterized by elemental analysis, NMR and IR spectroscopies, and X-ray crystal structure determination for complex 2.

关 键 词：四氢呋喃 钛络合物 胍配体 C-O键裂 合成 晶体结构 二异丙基酰胺 

分 类 号：O626.11[理学—有机化学]