The reaction mechanisms of Ti（~3F） ＋ CH2C12→CH2=TiCl2 and Ti（~3F） ＋ CHC13→HC÷TiCl3 were investigated with Gaussian 03 program package at the B3PW91/6-311＋＋G（d,p）level.The computational results reveale...The reaction mechanisms of Ti（~3F） ＋ CH2C12→CH2=TiCl2 and Ti（~3F） ＋ CHC13→HC÷TiCl3 were investigated with Gaussian 03 program package at the B3PW91/6-311＋＋G（d,p）level.The computational results revealed that：1） Both reaction systems are initiated by Ti（~3F） atom attacking the C atom of CH2C12 and CHCl3 to activate a C-Cl bond;2） Both reaction systems were carried out via triplet reaction channels;3） CH2=TiCl2 has singlet and triplet isomers,and the singlet one is more stable;4） The HOMO of CH2=TiCl2（S） illustrates a π-bonding interaction between C and Ti;5） Only singlet HC÷TiCl3 was located,and the Mulliken atomic spin densities show that the two single electrons are mostly on the C atom.展开更多
α-diketones and β-diketones react with Grignard reagents in the presence of a catalytic amount of Cp2TiCl2 to yield a-ketols and corresponding ketones respectively. Sulfoxides can be deoxygenated by Cp2TiCl2/Al syst...α-diketones and β-diketones react with Grignard reagents in the presence of a catalytic amount of Cp2TiCl2 to yield a-ketols and corresponding ketones respectively. Sulfoxides can be deoxygenated by Cp2TiCl2/Al system. The possible mechanisms are also discussed.展开更多
以1,3-二氯六甲基三硅烷相继与环戊二烯基钠、正丁基锂和四氯化钛作用合成了1,1′-(六甲基三硅撑)双环戊二烯基二氯化钛(1),1在氨基钠的存在下与对氯苯酚作用制得题目化合物(2).通过元素分析、~1H NMR 和 MS 鉴定了1与2的结构,并对2进行...以1,3-二氯六甲基三硅烷相继与环戊二烯基钠、正丁基锂和四氯化钛作用合成了1,1′-(六甲基三硅撑)双环戊二烯基二氯化钛(1),1在氨基钠的存在下与对氯苯酚作用制得题目化合物(2).通过元素分析、~1H NMR 和 MS 鉴定了1与2的结构,并对2进行 X 射线结构分析确证了其结构.2的晶体属单斜晶系的 P2_1/c 空间群.晶胞参数:a=1.0746(3),b=2.4865(7),c=1.2568(2)nm;β=113.42(2)°;V=3.08137nm^3;Z=4,D_σ(?)=1.305g·cm^(-3).化合物中三个硅原子的桥链发生明显扭曲.通过氧原子中心原子钛与苯环发生共轭,使整个分子形成共轭体系.展开更多
Reaction of Cp2TiCl2-Mg synthetic equivalent of practical Ti(II) reagent with propargyl alcohol derivatives affords allenyl titanium compounds in good yields.thus, providing an efficient and practical methods for synt...Reaction of Cp2TiCl2-Mg synthetic equivalent of practical Ti(II) reagent with propargyl alcohol derivatives affords allenyl titanium compounds in good yields.thus, providing an efficient and practical methods for synthesis of both allenyl and homopropargyl alcohols by the successive treatment with aldehydes and ketones.展开更多
Initiated by CP_2TiCl_2/Fe redox system,2-halotetrafluoroethyl iodides readily reacted with alkynes or alkenes to give 1:1 adducts in good to excellent yields.
基金financially supported by the National Natural Science Foundation of China(11174215)Natural Science Foundation of Shandong Province(ZR2012BL10)the University Science and Technology Project of Shandong Province(No.J13LD05)
文摘The reaction mechanisms of Ti（~3F） ＋ CH2C12→CH2=TiCl2 and Ti（~3F） ＋ CHC13→HC÷TiCl3 were investigated with Gaussian 03 program package at the B3PW91/6-311＋＋G（d,p）level.The computational results revealed that：1） Both reaction systems are initiated by Ti（~3F） atom attacking the C atom of CH2C12 and CHCl3 to activate a C-Cl bond;2） Both reaction systems were carried out via triplet reaction channels;3） CH2=TiCl2 has singlet and triplet isomers,and the singlet one is more stable;4） The HOMO of CH2=TiCl2（S） illustrates a π-bonding interaction between C and Ti;5） Only singlet HC÷TiCl3 was located,and the Mulliken atomic spin densities show that the two single electrons are mostly on the C atom.
基金Project (No. 20072033) supported by the National Natural Science Foundation of China and the Specialized Research Fund for the Doctoral Program of Higher Education Ministry, China
文摘α-diketones and β-diketones react with Grignard reagents in the presence of a catalytic amount of Cp2TiCl2 to yield a-ketols and corresponding ketones respectively. Sulfoxides can be deoxygenated by Cp2TiCl2/Al system. The possible mechanisms are also discussed.
文摘以1,3-二氯六甲基三硅烷相继与环戊二烯基钠、正丁基锂和四氯化钛作用合成了1,1′-(六甲基三硅撑)双环戊二烯基二氯化钛(1),1在氨基钠的存在下与对氯苯酚作用制得题目化合物(2).通过元素分析、~1H NMR 和 MS 鉴定了1与2的结构,并对2进行 X 射线结构分析确证了其结构.2的晶体属单斜晶系的 P2_1/c 空间群.晶胞参数:a=1.0746(3),b=2.4865(7),c=1.2568(2)nm;β=113.42(2)°;V=3.08137nm^3;Z=4,D_σ(?)=1.305g·cm^(-3).化合物中三个硅原子的桥链发生明显扭曲.通过氧原子中心原子钛与苯环发生共轭,使整个分子形成共轭体系.
文摘Reaction of Cp2TiCl2-Mg synthetic equivalent of practical Ti(II) reagent with propargyl alcohol derivatives affords allenyl titanium compounds in good yields.thus, providing an efficient and practical methods for synthesis of both allenyl and homopropargyl alcohols by the successive treatment with aldehydes and ketones.
文摘Initiated by CP_2TiCl_2/Fe redox system,2-halotetrafluoroethyl iodides readily reacted with alkynes or alkenes to give 1:1 adducts in good to excellent yields.
