通过4-[(2-吡啶基)乙亚胺基]-2-戊烯-2-醇(1)与[(Me3Si)2N]3Y(μ-Cl)Li(THF)3的反应,制备含吡啶基β-烯酮亚胺NNO型钇双胺基配合物(2),采用1 H NMR,13 C NMR,元素分析,X-ray和IR等对该配合物进行了表征,并探索了其在催化异戊二烯聚合中...通过4-[(2-吡啶基)乙亚胺基]-2-戊烯-2-醇(1)与[(Me3Si)2N]3Y(μ-Cl)Li(THF)3的反应,制备含吡啶基β-烯酮亚胺NNO型钇双胺基配合物(2),采用1 H NMR,13 C NMR,元素分析,X-ray和IR等对该配合物进行了表征,并探索了其在催化异戊二烯聚合中的应用.结果表明,配合物2在催化异戊二烯聚合方面有较好的催化活性和立体选择性.展开更多
The title compound {η^5：η^1-[（2-MeOC6H4）C3H6]CgH6}Li（DME） （DME=1,2-dimethoxy-ethylene） was synthesized by the treatment of 3-[（2-methoxyphenyl）-isopropyl]-indene with 1 equiv, of n-BuLi followed by the recr...The title compound {η^5：η^1-[（2-MeOC6H4）C3H6]CgH6}Li（DME） （DME=1,2-dimethoxy-ethylene） was synthesized by the treatment of 3-[（2-methoxyphenyl）-isopropyl]-indene with 1 equiv, of n-BuLi followed by the recrystallization from a mixed solution of toluene and DME. The compound crystallizes in orthorhombic system, pace group Pbca with a=14.5677（3）, b=15.54670（10）, c=18.7498（3）A°, Z=8, V=4246.45（11）A°^3, Dc=1.127 g/cm^3 and μ（MoKα）=0.072 mm^-1. The coordination geometry can be described as a distorted tetrahedron.展开更多
Reaction of sulfonylated binaphthol [2-hydroxy-2＇-tosyloxy-l,l-binaphthyl （la, Ts-Binol） or 2-hydroxy-2＇- （phenylsulfonyloxy）-l,l-binaphthyl （lb, Ps-Binol）] with 1 equiv, of ZnEt2 afforded zinc complexes [（Ys...Reaction of sulfonylated binaphthol [2-hydroxy-2＇-tosyloxy-l,l-binaphthyl （la, Ts-Binol） or 2-hydroxy-2＇- （phenylsulfonyloxy）-l,l-binaphthyl （lb, Ps-Binol）] with 1 equiv, of ZnEt2 afforded zinc complexes [（Ys-Binol）ZnEt]2 （2a） and [（Ps-Binol）ZnEt]2 （2b）. Further reaction of zinc complexes 2a and 2b with benzyl alco- hol （BnOH） gave the zinc benzyloxide [（Ts-Binol）2Zn2（OBn）2]2 （3a） and [（Ps-Binol）2Znz（OBn）2]2 （3b）. Alterna- tively, the zinc benzyloxides 3a and 3b could also be obtained by reaction of compound la or lb with Zn（OBn）2 （in situ reaction of ZnEt2 and BnOH）. The complexes were fully characterized by elemental analyses and spectroscopic analyses, and complexes 2a, 2b and 3a were further characterized by single-crystal X-ray analyses. The catalytic activities of these zinc complexes towards ring-opening polymerization of ε-caprolactone and D,L-lactide were studied.展开更多
Tetracoordinated lanthanide amides [(Me3Si)2N]3Ln (m-Cl)Li(THF)3 (Ln=La (1), Pr (2)) were synthesized by the reaction of anhydrous lanthanide(III) chlorides LnCl3 (Ln=La, Pr) with 3 equiv. of lithium bis(trimethylsily...Tetracoordinated lanthanide amides [(Me3Si)2N]3Ln (m-Cl)Li(THF)3 (Ln=La (1), Pr (2)) were synthesized by the reaction of anhydrous lanthanide(III) chlorides LnCl3 (Ln=La, Pr) with 3 equiv. of lithium bis(trimethylsilyl)amide (Me3Si)2NLi in THF, followed by recrystallization from toluene. Sublimation of 1 and 2 afforded the triscoordinate lanthanide amides [(Me3Si)2N]3Ln (Ln=La, Pr). The crystal structure of 2 was determined by X-ray diffraction analysis. The catalytic activity studies show that the tetracoordinate amides can be used as single-component MMA (methyl methacrylate) polymerization catalysts, while the triscoordinate amides showed poor activity on MMA polymerization under the same conditions.展开更多
文摘通过4-[(2-吡啶基)乙亚胺基]-2-戊烯-2-醇(1)与[(Me3Si)2N]3Y(μ-Cl)Li(THF)3的反应,制备含吡啶基β-烯酮亚胺NNO型钇双胺基配合物(2),采用1 H NMR,13 C NMR,元素分析,X-ray和IR等对该配合物进行了表征,并探索了其在催化异戊二烯聚合中的应用.结果表明,配合物2在催化异戊二烯聚合方面有较好的催化活性和立体选择性.
基金This work was supported by the National Natural Science Foundation of China (No. 20472001), the program for NCET (NCET-04-590), and the Excellent Young Scholars foundation of Anhui Province (04046079) and a grant from Anhui Education Department (2005hbz06)
文摘The title compound {η^5：η^1-[（2-MeOC6H4）C3H6]CgH6}Li（DME） （DME=1,2-dimethoxy-ethylene） was synthesized by the treatment of 3-[（2-methoxyphenyl）-isopropyl]-indene with 1 equiv, of n-BuLi followed by the recrystallization from a mixed solution of toluene and DME. The compound crystallizes in orthorhombic system, pace group Pbca with a=14.5677（3）, b=15.54670（10）, c=18.7498（3）A°, Z=8, V=4246.45（11）A°^3, Dc=1.127 g/cm^3 and μ（MoKα）=0.072 mm^-1. The coordination geometry can be described as a distorted tetrahedron.
文摘Reaction of sulfonylated binaphthol [2-hydroxy-2＇-tosyloxy-l,l-binaphthyl （la, Ts-Binol） or 2-hydroxy-2＇- （phenylsulfonyloxy）-l,l-binaphthyl （lb, Ps-Binol）] with 1 equiv, of ZnEt2 afforded zinc complexes [（Ys-Binol）ZnEt]2 （2a） and [（Ps-Binol）ZnEt]2 （2b）. Further reaction of zinc complexes 2a and 2b with benzyl alco- hol （BnOH） gave the zinc benzyloxide [（Ts-Binol）2Zn2（OBn）2]2 （3a） and [（Ps-Binol）2Znz（OBn）2]2 （3b）. Alterna- tively, the zinc benzyloxides 3a and 3b could also be obtained by reaction of compound la or lb with Zn（OBn）2 （in situ reaction of ZnEt2 and BnOH）. The complexes were fully characterized by elemental analyses and spectroscopic analyses, and complexes 2a, 2b and 3a were further characterized by single-crystal X-ray analyses. The catalytic activities of these zinc complexes towards ring-opening polymerization of ε-caprolactone and D,L-lactide were studied.
基金Project supported by the National Natural Science Foundation of China (Nos. 20072001 and 20271003) the Excellent Young Scholars Foundation of Anhui Province and Education Department of Anhui Province.
文摘Tetracoordinated lanthanide amides [(Me3Si)2N]3Ln (m-Cl)Li(THF)3 (Ln=La (1), Pr (2)) were synthesized by the reaction of anhydrous lanthanide(III) chlorides LnCl3 (Ln=La, Pr) with 3 equiv. of lithium bis(trimethylsilyl)amide (Me3Si)2NLi in THF, followed by recrystallization from toluene. Sublimation of 1 and 2 afforded the triscoordinate lanthanide amides [(Me3Si)2N]3Ln (Ln=La, Pr). The crystal structure of 2 was determined by X-ray diffraction analysis. The catalytic activity studies show that the tetracoordinate amides can be used as single-component MMA (methyl methacrylate) polymerization catalysts, while the triscoordinate amides showed poor activity on MMA polymerization under the same conditions.
