In this work, we report a theoretical exploration of the ground-state electronic structures and molecular vibrational properties of a series of binuclear zirconium complexes in the framework of density functional theo...In this work, we report a theoretical exploration of the ground-state electronic structures and molecular vibrational properties of a series of binuclear zirconium complexes in the framework of density functional theory （DFT） employing the B3LYP hybrid functional. The calculated results reveal that the electronic structure of the complex [（η^5-C5Me5）2Zr]2（μ^2, η^2, η^2-N2） is unfavorable for hydrogenation due to the exclusion of side-on dinitrogen in the LUMO＋ 1 molecular orbital as compared with the reactant 1 [（η^5-C5Me4H）2Zr]2（μ2,η^2,η^2-N2）. Besides, the structural feature of the hypothetical intermediate 1′, [（η^5C5Me4H）2Zr]2（μ2,η^2, η^2-N2）-n2, clearly implies the possibility of further hydrogenation. In addition, the distinguishing of vibrational modes of experimental intermediate 2, [（η^5-C5Me4H）2ZrH]2（μ2,η^2,η^2-N2H2）, indicates that the asymmetric stretching of Zr-N and Zr-H leads to dissociation. Moreover, the vibrational intensity of Zr-H is stronger than that of Zr-N. Therefore, it can be predicted that excess hydrogen atmosphere is necessary to ensure the dissociation of Zr-N bonds.展开更多
Bis(8-quinolinolato)zirconium dichloride (Ox)2ZrCl2 (Ox- = 8-quinolinolato) was found active for ethylene oligomerization with a high selectivity of 84~94% to C4~C10 olefins at 70~100C under the pressure of 1.8 MPa us...Bis(8-quinolinolato)zirconium dichloride (Ox)2ZrCl2 (Ox- = 8-quinolinolato) was found active for ethylene oligomerization with a high selectivity of 84~94% to C4~C10 olefins at 70~100C under the pressure of 1.8 MPa using Et2AlCl as a co-catalyst (Al/Zr = 60).展开更多
Metallocene complex Cp tt 2ZrCl 2 (Cp tt =η 5 1,3 t Bu 2 C 5 H 3 ) (1) has been prepared from the reaction of LiCp tt with ZrCl 4 in good yield. Reactio...Metallocene complex Cp tt 2ZrCl 2 (Cp tt =η 5 1,3 t Bu 2 C 5 H 3 ) (1) has been prepared from the reaction of LiCp tt with ZrCl 4 in good yield. Reactions of 1 with dilithium dichalcogenolate o carboranes afforded new type of half sandwich compounds with dichalcogenolate o carboranyl ligands, [Li(THF) 4 ][Cp tt Zr(E 2 C 2 B 10 H 10 ) 2 ] (E=S, 2a; E=Se, 2b) in which only one cyclopentadienyl ring ligand existed. Complexes 1 and 2a were structurally characterized by X ray analyses. In complex 2a, the Zr(IV) ion is η 5 bound to one 1,3 di tert cyclopentadienyl ring and σ bound to four μ 2 sulfur atoms of two dithio carboranes. The zirconium atom and four sulfur atoms form a distorted pyramid. The coordination sphere around the zirconium atom resembles in a piano stool structure with four legs of sulfur atoms and the fulcrum at the zirconium atom.展开更多
Complexes （R^1Cp）（R^2Ind）ZrCl2, the catalysts previously reported active for ethylene polymerization showed high activity in ethylene/1-hexene copolymerization and propylene polymerization in the presence of MAO. ...Complexes （R^1Cp）（R^2Ind）ZrCl2, the catalysts previously reported active for ethylene polymerization showed high activity in ethylene/1-hexene copolymerization and propylene polymerization in the presence of MAO. The content of 1-hexene in copolymers ranged from 1.2% to 3.2%. In propylene polymerization the complex 1 showed the highest activity, up to 1.2×10^6 g of polypropylene per mol of catalyst per hour. Based on the analysis of NMR spectral data, the relationships between complex structures and polymerization results were explored.展开更多
An unbridged zirconocene complex bis(1,2-diphenylcyclopentadienyl)zirconium dichloride [(1,2-Ph2-C5H3)2ZrCl2] 1 has been synthesized and structurally characterized. When activated by MAO, 1 produces ultra-high molecul...An unbridged zirconocene complex bis(1,2-diphenylcyclopentadienyl)zirconium dichloride [(1,2-Ph2-C5H3)2ZrCl2] 1 has been synthesized and structurally characterized. When activated by MAO, 1 produces ultra-high molecular weight polyethylene with high melting transition temperature, as well as atactic oligopropylene with average molecular weight of ~1150 g mol-1.展开更多
A novel bis(8-oxide quinoline)zironium phthalocyanine [(OQ)2 Zr Pc] with two 8-oxide quinolone anions at the same axial positions has been successfully synthesized and its chemical structure has been assigned by the 1...A novel bis(8-oxide quinoline)zironium phthalocyanine [(OQ)2 Zr Pc] with two 8-oxide quinolone anions at the same axial positions has been successfully synthesized and its chemical structure has been assigned by the 1 H NMR, MS and two-dimensional correlation infrared(2D-IR) spectroscopy as well as by single-crystal X-ray structural analysis. It possessed a moderately effective nonlinear absorption coefficient βeff of 6.69×10-14cm/GW at 532 nm in DMF solution, implying it is a promising candidate for nonlinear optical materials.展开更多
Zirconium proline-N-methylphosphonate-phosphate (α-ZPMPP) was prepared in the presence of HF for the first time. The a-ZPMPP sample is highly crystallized with interlayer distance of 1.52 nm. The interlayer distance ...Zirconium proline-N-methylphosphonate-phosphate (α-ZPMPP) was prepared in the presence of HF for the first time. The a-ZPMPP sample is highly crystallized with interlayer distance of 1.52 nm. The interlayer distance of complex of α-ZPMPP with n-butylamine (α-ZPMPP-BA) is in 0.45 nm larger than that of α-ZPMPP. The α-ZPMPP possesses different intercalation behavior of host-vip compound from α-ZP.展开更多
基金Supported by the National Natural Science Foundation of China (No. 20573114)MOST Project of 2006DFA43020 and 2007CB815307
文摘In this work, we report a theoretical exploration of the ground-state electronic structures and molecular vibrational properties of a series of binuclear zirconium complexes in the framework of density functional theory （DFT） employing the B3LYP hybrid functional. The calculated results reveal that the electronic structure of the complex [（η^5-C5Me5）2Zr]2（μ^2, η^2, η^2-N2） is unfavorable for hydrogenation due to the exclusion of side-on dinitrogen in the LUMO＋ 1 molecular orbital as compared with the reactant 1 [（η^5-C5Me4H）2Zr]2（μ2,η^2,η^2-N2）. Besides, the structural feature of the hypothetical intermediate 1′, [（η^5C5Me4H）2Zr]2（μ2,η^2, η^2-N2）-n2, clearly implies the possibility of further hydrogenation. In addition, the distinguishing of vibrational modes of experimental intermediate 2, [（η^5-C5Me4H）2ZrH]2（μ2,η^2,η^2-N2H2）, indicates that the asymmetric stretching of Zr-N and Zr-H leads to dissociation. Moreover, the vibrational intensity of Zr-H is stronger than that of Zr-N. Therefore, it can be predicted that excess hydrogen atmosphere is necessary to ensure the dissociation of Zr-N bonds.
基金We are gratefully acknowledge the National Natural Science Foundation of China(Grant no.20173006)for financial support of this research
文摘Bis(8-quinolinolato)zirconium dichloride (Ox)2ZrCl2 (Ox- = 8-quinolinolato) was found active for ethylene oligomerization with a high selectivity of 84~94% to C4~C10 olefins at 70~100C under the pressure of 1.8 MPa using Et2AlCl as a co-catalyst (Al/Zr = 60).
基金theNationalNaturalScienceFoundationofChina (No .2 992 5 10 1)theMajorStateBasicResearchDevelopmentProgram (No .G19990 64 80 0 )
文摘Metallocene complex Cp tt 2ZrCl 2 (Cp tt =η 5 1,3 t Bu 2 C 5 H 3 ) (1) has been prepared from the reaction of LiCp tt with ZrCl 4 in good yield. Reactions of 1 with dilithium dichalcogenolate o carboranes afforded new type of half sandwich compounds with dichalcogenolate o carboranyl ligands, [Li(THF) 4 ][Cp tt Zr(E 2 C 2 B 10 H 10 ) 2 ] (E=S, 2a; E=Se, 2b) in which only one cyclopentadienyl ring ligand existed. Complexes 1 and 2a were structurally characterized by X ray analyses. In complex 2a, the Zr(IV) ion is η 5 bound to one 1,3 di tert cyclopentadienyl ring and σ bound to four μ 2 sulfur atoms of two dithio carboranes. The zirconium atom and four sulfur atoms form a distorted pyramid. The coordination sphere around the zirconium atom resembles in a piano stool structure with four legs of sulfur atoms and the fulcrum at the zirconium atom.
基金Project supported by the Major State Basic Research Development Program（No.G1999064801） the National Natural Science Foundation of China （No. 20372022） and the Research Fund for the Doctoral Program of Higher Education （No. 20020251002）.
文摘Complexes （R^1Cp）（R^2Ind）ZrCl2, the catalysts previously reported active for ethylene polymerization showed high activity in ethylene/1-hexene copolymerization and propylene polymerization in the presence of MAO. The content of 1-hexene in copolymers ranged from 1.2% to 3.2%. In propylene polymerization the complex 1 showed the highest activity, up to 1.2×10^6 g of polypropylene per mol of catalyst per hour. Based on the analysis of NMR spectral data, the relationships between complex structures and polymerization results were explored.
文摘An unbridged zirconocene complex bis(1,2-diphenylcyclopentadienyl)zirconium dichloride [(1,2-Ph2-C5H3)2ZrCl2] 1 has been synthesized and structurally characterized. When activated by MAO, 1 produces ultra-high molecular weight polyethylene with high melting transition temperature, as well as atactic oligopropylene with average molecular weight of ~1150 g mol-1.
基金supported by the Natural Science Foundation of Fujian Province(2018J01431 and 2018J01690)Research Foundation of Education Bureau of Fujian Province(JT180813)
文摘A novel bis(8-oxide quinoline)zironium phthalocyanine [(OQ)2 Zr Pc] with two 8-oxide quinolone anions at the same axial positions has been successfully synthesized and its chemical structure has been assigned by the 1 H NMR, MS and two-dimensional correlation infrared(2D-IR) spectroscopy as well as by single-crystal X-ray structural analysis. It possessed a moderately effective nonlinear absorption coefficient βeff of 6.69×10-14cm/GW at 532 nm in DMF solution, implying it is a promising candidate for nonlinear optical materials.
文摘Zirconium proline-N-methylphosphonate-phosphate (α-ZPMPP) was prepared in the presence of HF for the first time. The a-ZPMPP sample is highly crystallized with interlayer distance of 1.52 nm. The interlayer distance of complex of α-ZPMPP with n-butylamine (α-ZPMPP-BA) is in 0.45 nm larger than that of α-ZPMPP. The α-ZPMPP possesses different intercalation behavior of host-vip compound from α-ZP.
