A novel anionic organotin(Ⅳ) complex {[(pClCHCH)Sn(HO)(Cl)OCOCH(O)CH(O)COSn(HO)(Cl)(p-ClCHCH)]·2(HNEt)}(1) was synthesized by the reaction of di(p-chlorobenzy)tin dichloride with the D-tartaric acid in 2:1 molar...A novel anionic organotin(Ⅳ) complex {[(pClCHCH)Sn(HO)(Cl)OCOCH(O)CH(O)COSn(HO)(Cl)(p-ClCHCH)]·2(HNEt)}(1) was synthesized by the reaction of di(p-chlorobenzy)tin dichloride with the D-tartaric acid in 2:1 molar in the presence of an organic base triethylamine. The structure was characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction. It crystallizes in triclinic, P1 space group, with a = 0.7067(1), b = 1.9762(3), c = 2.2383(3) nm, α = 91.544(2)°, β = 90.075(2)°, γ = 90.110(2)°, V = 3.1247(7) nm~3, Z = 3, Dc = 1.621 g/cm~3, m(Mo Kα) = 16.29 cm–1, F(000) = 1530, R = 0.0394, wR = 0.1092,(Δρ)max = 1224 and(Δρ)min = –840 e/nm~3. The stabilities, orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been carefully investigated with quantum chemistry calculation. In addition, the in vitro antitumor activity suggested that 1 had stronger inhibitory activity on H460, MCF7 than on A549.展开更多
Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of dif...Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [( i -Pr)_2NH_2] [PhSn( μ 2-SCH_2COO)_2] was determined by X-ray diffraction. In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a =1.1766(11) nm, b =1.3144(14) nm, c =1.3336(15) nm,β =90° and Z =4.展开更多
The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, ...The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, which contains both dibenzhydryl and phenyl groups, was determined by X-ray crystallography. The compound has a pseudo-tetrahedral geometry at the Ni center, showing pseudo-C2-symmetry. Upon activation with modified methylaluminoxane (MMAO), Ni1 exhibits high catalytic activity up to 1.02 × 107 g PE (mol Ni h)−1 toward ethylene polymerization, enabling the synthesis of high molecular weight branched polyethylene. The molecular weights and branching densities could be tuned over a very wide range. The polymerization results indicated the possibility of precise microstructure control, depending on the polymerization temperature. The branching densities were decreased with increasing the polymerization temperature.展开更多
A new isopolyoxovanadate [Ni(1,10′-phen) 3] 2 [V Ⅳ 2V Ⅴ 8O 26] was hydrothermally synthesized and structurally characterized by the single crystal X-ray diffraction. The compound crystallizes in orthorhombic system...A new isopolyoxovanadate [Ni(1,10′-phen) 3] 2 [V Ⅳ 2V Ⅴ 8O 26] was hydrothermally synthesized and structurally characterized by the single crystal X-ray diffraction. The compound crystallizes in orthorhombic system, space group Pbcn with a=1.362 9(3) nm, b=2.215 6(4) nm, c= 2.571 2(4) nm, V=7.764(2) nm 3, Z=4, R=0.040 3, wR 2=0.044 6. The compound exhibits an unusual empty ellipsoidal cage, which is constructed by eight {V ⅤO 4} tetrahedra and two {V ⅣO 5} square pyramids via corner-sharing modes. The chiral [Ni(1,10′-phen) 3] 2+ complexes act as the counter cations.展开更多
Tetra\{\[4\|carboxymethoxyphenyl\]\}porphyrin copper(Ⅱ), nickel(Ⅱ), zinc(Ⅱ) complex and their dibutyltin(Ⅳ) ester derivatives have been synthesized and characterized. The equilibrium constants of the aggregation o...Tetra\{\[4\|carboxymethoxyphenyl\]\}porphyrin copper(Ⅱ), nickel(Ⅱ), zinc(Ⅱ) complex and their dibutyltin(Ⅳ) ester derivatives have been synthesized and characterized. The equilibrium constants of the aggregation of the metal porphyrin and the equilibrium constant of the π\|π coordination with phenothoroline have been measured by using UV\|Vis titration method. The results show that the equilibrium constants decrease in the order of K \-\{CuP\}> K \-\{NiP\}> K \-\{ZnP\}. The vitro anti\|tumor activities of the dibutyltin(Ⅳ) metal porphyrinate has some relation with the ability of aggregation and coordination with ligand of the metal porphyrin.展开更多
A new complex [Ni（en）3]4[HVⅣ12VⅤ6O42（PO4）] has been hydrothermally synthesize d and characterized by X-Ray diffraction,IR and Elemental analysis.Single crystal X-ray analysis indicates that this compoud cry stal...A new complex [Ni（en）3]4[HVⅣ12VⅤ6O42（PO4）] has been hydrothermally synthesize d and characterized by X-Ray diffraction,IR and Elemental analysis.Single crystal X-ray analysis indicates that this compoud cry stallizes in cubic system,space group Im3m with a=17.4081（2）*!,V=5275.38（10）*! 3 ,R=0.0420,w R=0.1055,Z =2,D c =1.663g·cm -3 ,μ=2.297mm -1 ,F（000）=2636.The crystal structure consis ts of[Ni （en） 3 ] 2+ cations and{HV 18 O 42 （PO 4 ）} 8- cluster anion which construct from 18{VO 5 }.square pyramids.The VO 5 pyramids joined each other to form a {V 18 O 42 }cage hosting a tetrahedral{PO 4 } 3- moiety with disordered oxygen atoms .CCDC:185574.展开更多
The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous met...The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous methanol. The crystal structures of I and II were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Ni（C18H45N3O3）]Cl2, orthorhombic, P212121, a = 11.2807（9）, b = 14.7115（11）, c = 16.3580（13） A, V = 2714.7（4） A3, Z = 4, Pcalcd = 1.177 Mg/m3, the final R = 0.0407, and 16539 reflections observed with I 〉 2σ（/）; For II： [Co（C45HI08N6015）], trigonal, R3：H, a = 23.981（3）, b =23.981（3）, c = 10.8925（15） A, γ = 120°, V = 5425.1（14） A3, Z = 3, Pcalcd = 1.002 Mg/m3, the final R = 0.0625 for 16556 observed reflections with I 〉 2σ（I）. The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by IH NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.展开更多
基金Supported by the Open Fund Project innovation platform of Key Laboratory of Higher Educational Institutions of Hunan Province(GN16K01)Scientific&Technological Projects of Hengyang(2016KL03)+1 种基金Aid programs for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Provincethe Key Discipline of Hunan Province,Project funding for research and innovation experiment of university students in Hunan Province
文摘A novel anionic organotin(Ⅳ) complex {[(pClCHCH)Sn(HO)(Cl)OCOCH(O)CH(O)COSn(HO)(Cl)(p-ClCHCH)]·2(HNEt)}(1) was synthesized by the reaction of di(p-chlorobenzy)tin dichloride with the D-tartaric acid in 2:1 molar in the presence of an organic base triethylamine. The structure was characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction. It crystallizes in triclinic, P1 space group, with a = 0.7067(1), b = 1.9762(3), c = 2.2383(3) nm, α = 91.544(2)°, β = 90.075(2)°, γ = 90.110(2)°, V = 3.1247(7) nm~3, Z = 3, Dc = 1.621 g/cm~3, m(Mo Kα) = 16.29 cm–1, F(000) = 1530, R = 0.0394, wR = 0.1092,(Δρ)max = 1224 and(Δρ)min = –840 e/nm~3. The stabilities, orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been carefully investigated with quantum chemistry calculation. In addition, the in vitro antitumor activity suggested that 1 had stronger inhibitory activity on H460, MCF7 than on A549.
文摘Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [( i -Pr)_2NH_2] [PhSn( μ 2-SCH_2COO)_2] was determined by X-ray diffraction. In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a =1.1766(11) nm, b =1.3144(14) nm, c =1.3336(15) nm,β =90° and Z =4.
文摘The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, which contains both dibenzhydryl and phenyl groups, was determined by X-ray crystallography. The compound has a pseudo-tetrahedral geometry at the Ni center, showing pseudo-C2-symmetry. Upon activation with modified methylaluminoxane (MMAO), Ni1 exhibits high catalytic activity up to 1.02 × 107 g PE (mol Ni h)−1 toward ethylene polymerization, enabling the synthesis of high molecular weight branched polyethylene. The molecular weights and branching densities could be tuned over a very wide range. The polymerization results indicated the possibility of precise microstructure control, depending on the polymerization temperature. The branching densities were decreased with increasing the polymerization temperature.
文摘A new isopolyoxovanadate [Ni(1,10′-phen) 3] 2 [V Ⅳ 2V Ⅴ 8O 26] was hydrothermally synthesized and structurally characterized by the single crystal X-ray diffraction. The compound crystallizes in orthorhombic system, space group Pbcn with a=1.362 9(3) nm, b=2.215 6(4) nm, c= 2.571 2(4) nm, V=7.764(2) nm 3, Z=4, R=0.040 3, wR 2=0.044 6. The compound exhibits an unusual empty ellipsoidal cage, which is constructed by eight {V ⅤO 4} tetrahedra and two {V ⅣO 5} square pyramids via corner-sharing modes. The chiral [Ni(1,10′-phen) 3] 2+ complexes act as the counter cations.
文摘Tetra\{\[4\|carboxymethoxyphenyl\]\}porphyrin copper(Ⅱ), nickel(Ⅱ), zinc(Ⅱ) complex and their dibutyltin(Ⅳ) ester derivatives have been synthesized and characterized. The equilibrium constants of the aggregation of the metal porphyrin and the equilibrium constant of the π\|π coordination with phenothoroline have been measured by using UV\|Vis titration method. The results show that the equilibrium constants decrease in the order of K \-\{CuP\}> K \-\{NiP\}> K \-\{ZnP\}. The vitro anti\|tumor activities of the dibutyltin(Ⅳ) metal porphyrinate has some relation with the ability of aggregation and coordination with ligand of the metal porphyrin.
文摘A new complex [Ni（en）3]4[HVⅣ12VⅤ6O42（PO4）] has been hydrothermally synthesize d and characterized by X-Ray diffraction,IR and Elemental analysis.Single crystal X-ray analysis indicates that this compoud cry stallizes in cubic system,space group Im3m with a=17.4081（2）*!,V=5275.38（10）*! 3 ,R=0.0420,w R=0.1055,Z =2,D c =1.663g·cm -3 ,μ=2.297mm -1 ,F（000）=2636.The crystal structure consis ts of[Ni （en） 3 ] 2+ cations and{HV 18 O 42 （PO 4 ）} 8- cluster anion which construct from 18{VO 5 }.square pyramids.The VO 5 pyramids joined each other to form a {V 18 O 42 }cage hosting a tetrahedral{PO 4 } 3- moiety with disordered oxygen atoms .CCDC:185574.
文摘The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous methanol. The crystal structures of I and II were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Ni（C18H45N3O3）]Cl2, orthorhombic, P212121, a = 11.2807（9）, b = 14.7115（11）, c = 16.3580（13） A, V = 2714.7（4） A3, Z = 4, Pcalcd = 1.177 Mg/m3, the final R = 0.0407, and 16539 reflections observed with I 〉 2σ（/）; For II： [Co（C45HI08N6015）], trigonal, R3：H, a = 23.981（3）, b =23.981（3）, c = 10.8925（15） A, γ = 120°, V = 5425.1（14） A3, Z = 3, Pcalcd = 1.002 Mg/m3, the final R = 0.0625 for 16556 observed reflections with I 〉 2σ（I）. The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by IH NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.
