As a discovery of C\_C coupling and amine elimination reaction by treatment of \{6\|dimethylamino\|6\|methylfulvene\} with zirconium tetrachloride, experiments using amino\|substituted benzofulvene 1a or aminopentaful...As a discovery of C\_C coupling and amine elimination reaction by treatment of \{6\|dimethylamino\|6\|methylfulvene\} with zirconium tetrachloride, experiments using amino\|substituted benzofulvene 1a or aminopentafulvene 2a, instead of 6\|dimethylamino\|6\|methylfulvene, gave \{bis\{\[1\|(dimethylamino)\}\}ethenyl\|indenyl\]zirconium dichloride 1c which was characterized by X\|ray diffraction as monoclinic, space group \%C2/c\%, \%a\%=2.028 8(4) nm, \%b\%=0.981 7(2) nm, \%c\%=1.458 9(3) nm, \%β\%=115.73(3)°, \%V\%=2.617 5(9) nm\+3, \%Z\%=4, \%R\%=0.072 3, and bis\[(1\|methyl\|4,5\|dihydro\|2\|pyrrolnyl)cyclopentadienyl\]zirconium dichloride 2c as triclinic, space group \%P\%1, \%a\%=0.807 49(16) nm, \%b\%=\{0.943 40(19)\} nm, \%c\%=\{1.423 8(3)\} nm, \%α\%=91.04(3), \%β\%=97.41(3), \%γ\%=106.68(3)°, \%V\%=1.028 6(4) nm\+3, \%Z\%=2, \%R\%=0.080 0.展开更多
The complexes of dimethylcyclopentadienyl dichlorotitanium(Ⅳ)and salicytic acid,sulfhydryl salicylic acid,5-nitrosalicylic acid,3,5-dinitro salicylic acid have been prepared in aqueous-phase.The structures have been ...The complexes of dimethylcyclopentadienyl dichlorotitanium(Ⅳ)and salicytic acid,sulfhydryl salicylic acid,5-nitrosalicylic acid,3,5-dinitro salicylic acid have been prepared in aqueous-phase.The structures have been determined by elemental analysis,IR and 1HNMR spectra. It’s approved that (MeCp) 2TiCl 2-acetylacetone complex reacts with sodium of salicylic acid or substituted derivatives in aqueous-phase,and the results depend on the pH of salicylate solution,concentration and temperature.The best condition of the preparation of dimethylcyclopentadienyl salicylatotitanium(Ⅳ)complexes is that:the molar ration of (MeCp) 2TiCl 2 and substituted salicylic acid is 1:1;the pH being controlled in 6 0-7 5.The disalicylato derivatives of dimethylcyclopentadienyl titanium(Ⅳ)are whereby where by (MeCp) 2TiCl 2 and substituted salicylic acid are close in the molar ratio of 1 to 2,and the pH is 3.5-4.5.In all the preparations,the temperature is at 0℃ and the molar concentration of substituted salicylic acid is 0.04 mol/L.The mechanism of the reaction was also discussed.展开更多
Four titanocene complexes were prepared in aqueous or two - phase medium by the reaction of benzoylacetone titanocene with substituted salicylic acid,respectively.Based on the UV - Vis spectra,we studied the accelerat...Four titanocene complexes were prepared in aqueous or two - phase medium by the reaction of benzoylacetone titanocene with substituted salicylic acid,respectively.Based on the UV - Vis spectra,we studied the accelerating effect of the benzoylacetone on the reaction rate quantificationally.The results demonstrated that the presence of it not only stabilizes the “ Cp 2 Ti ” species and accordingly makes pH value of the aqueous solution of substituted salicylic acid increased but also prompts the reaction due to the presence of its conjugation structure and oleophyllic group.Furthermore,the presence of benzoylacetone is in favor of the simplification of the products.展开更多
文摘As a discovery of C\_C coupling and amine elimination reaction by treatment of \{6\|dimethylamino\|6\|methylfulvene\} with zirconium tetrachloride, experiments using amino\|substituted benzofulvene 1a or aminopentafulvene 2a, instead of 6\|dimethylamino\|6\|methylfulvene, gave \{bis\{\[1\|(dimethylamino)\}\}ethenyl\|indenyl\]zirconium dichloride 1c which was characterized by X\|ray diffraction as monoclinic, space group \%C2/c\%, \%a\%=2.028 8(4) nm, \%b\%=0.981 7(2) nm, \%c\%=1.458 9(3) nm, \%β\%=115.73(3)°, \%V\%=2.617 5(9) nm\+3, \%Z\%=4, \%R\%=0.072 3, and bis\[(1\|methyl\|4,5\|dihydro\|2\|pyrrolnyl)cyclopentadienyl\]zirconium dichloride 2c as triclinic, space group \%P\%1, \%a\%=0.807 49(16) nm, \%b\%=\{0.943 40(19)\} nm, \%c\%=\{1.423 8(3)\} nm, \%α\%=91.04(3), \%β\%=97.41(3), \%γ\%=106.68(3)°, \%V\%=1.028 6(4) nm\+3, \%Z\%=2, \%R\%=0.080 0.
文摘The complexes of dimethylcyclopentadienyl dichlorotitanium(Ⅳ)and salicytic acid,sulfhydryl salicylic acid,5-nitrosalicylic acid,3,5-dinitro salicylic acid have been prepared in aqueous-phase.The structures have been determined by elemental analysis,IR and 1HNMR spectra. It’s approved that (MeCp) 2TiCl 2-acetylacetone complex reacts with sodium of salicylic acid or substituted derivatives in aqueous-phase,and the results depend on the pH of salicylate solution,concentration and temperature.The best condition of the preparation of dimethylcyclopentadienyl salicylatotitanium(Ⅳ)complexes is that:the molar ration of (MeCp) 2TiCl 2 and substituted salicylic acid is 1:1;the pH being controlled in 6 0-7 5.The disalicylato derivatives of dimethylcyclopentadienyl titanium(Ⅳ)are whereby where by (MeCp) 2TiCl 2 and substituted salicylic acid are close in the molar ratio of 1 to 2,and the pH is 3.5-4.5.In all the preparations,the temperature is at 0℃ and the molar concentration of substituted salicylic acid is 0.04 mol/L.The mechanism of the reaction was also discussed.
文摘Four titanocene complexes were prepared in aqueous or two - phase medium by the reaction of benzoylacetone titanocene with substituted salicylic acid,respectively.Based on the UV - Vis spectra,we studied the accelerating effect of the benzoylacetone on the reaction rate quantificationally.The results demonstrated that the presence of it not only stabilizes the “ Cp 2 Ti ” species and accordingly makes pH value of the aqueous solution of substituted salicylic acid increased but also prompts the reaction due to the presence of its conjugation structure and oleophyllic group.Furthermore,the presence of benzoylacetone is in favor of the simplification of the products.
基金This work is supported by the Chinese National Natural Science Foundation (No. 2 0 173 0 0 6and 2 0 12 80 0 5 ) Science Founda-tion of L iaoning(No.2 0 0 110 2 0 89) and the Swedish Research Council
