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
A facile EDTA （ethylene diamine tetraacetic acid） complexing technique has been successfully employed to prepare La2Mo2O9 nanoparticles. The as-synthesized products are characterized by X-ray diffraction （XRD）, sc...A facile EDTA （ethylene diamine tetraacetic acid） complexing technique has been successfully employed to prepare La2Mo2O9 nanoparticles. The as-synthesized products are characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, and Fourier transform infrared spectroscopy （FT-IR）. The results show that a homogeneous transparent gel can be obtained with EDTA as the organic complexing reagent under the pH value of 3.0. Further thermal decomposition of the as-synthesized transparent gel by increasing the temperature up to 600℃ for 3 h results in the formation of La2Mo2O9 nanoparticles with a crystal size of about 30 nm. Moreover, the nanoparticles tend to form micrometer-sized aggregates with a three-dimensional network structure, which shows promising applications in solid oxide fuel cells （SOFC）, catalysts and so on.展开更多
The synthesis and characterization of two chiral fullerene complexes (+)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(RR))] 1 and (-)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(SS))] 2 were described. The CD spectra of 1 and 2 inth...The synthesis and characterization of two chiral fullerene complexes (+)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(RR))] 1 and (-)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(SS))] 2 were described. The CD spectra of 1 and 2 inthe visible range show weak Cotton effects, which are approximately of mirror image, indicatingthat the appended pineno-groups with opposite chirality in bipyridines can perturb the fullerenechromophores through the molybdenum centers and lead to induced CD effects.展开更多
The solid state reaction of MoCl3. 3H2O with 8--hydroxylquinine givesthe title compound MoO2, (C9H6NO)2. The crystallographic data for C18,H12,N2O4.Mo=monoclinic, space group C2/c, a= 13. 357(4), b= 9. 434(2), c= 13. ...The solid state reaction of MoCl3. 3H2O with 8--hydroxylquinine givesthe title compound MoO2, (C9H6NO)2. The crystallographic data for C18,H12,N2O4.Mo=monoclinic, space group C2/c, a= 13. 357(4), b= 9. 434(2), c= 13. 540(5) A, β=109. 39(6)°, V= 1609 (2) A3, Z= 4, M.= 416. 24, D.= 1. 72 g/cm3, μ(MoKa) 8. 19 cm-l, F(000) = 832, R= 0. 049 and Rw= 0. 058 for 1118 observed refletions.The Mo atom is,coordinated by two N atoms and two O atoms from two 8-hydroxylquinine and other two terminal O atoms, forming octahedral coordination geometry.展开更多
The 1H and 13C NMR spectra of the dinuclear complexes of molybdenum(VI) withethylenediaminetetraacetic acid ([Mo(VI)]2-EDTA) and 3,12-bis(carboxymethyl)-6.9-dioxa-3,12-diazatetra-decanedioic acid(tMo(VI)]2-EGTA) at va...The 1H and 13C NMR spectra of the dinuclear complexes of molybdenum(VI) withethylenediaminetetraacetic acid ([Mo(VI)]2-EDTA) and 3,12-bis(carboxymethyl)-6.9-dioxa-3,12-diazatetra-decanedioic acid(tMo(VI)]2-EGTA) at various temperatures were measured. The solutionstructure of the two dinuclear complexes was determined and the possible exchange process of theisomers is suggested展开更多
Abstract The complexes [M（CO）;（CH;CN）;]（M=Mo, W）react with an equimolar quantity ofPhSnCl;in dichloromethane at room tempreture to afford new heterobinuclearcomplexes [PhCl;SnM（Cl）(CO);（CH;CN）;] [M=Mo（1）; ...Abstract The complexes [M（CO）;（CH;CN）;]（M=Mo, W）react with an equimolar quantity ofPhSnCl;in dichloromethane at room tempreture to afford new heterobinuclearcomplexes [PhCl;SnM（Cl）(CO);（CH;CN）;] [M=Mo（1）; W（2）]. The complexes reactwith two equivalents of PR;R’（R=Ph, R’=Ph, Me; R=Cy, R’=H） to yield stablecomplexes [PhCl;SnM（Cl）(CO);（PR;R’）;]. Reaction of[PhCl;SnM（Cl）(CO);（CH;CN）;]with one equivalent of PPh;（CH;）nPPh;（n=I,2） or bulky phosphine ligands PBu;Clin dichloromethane at room tempreture to give [PhCl;SnMo（Cl）(CO);{PPh;（CH;）n-PPh;}] .CH;Cl;, [PhCl;SnMo（Cl）(CO);PBu;Cl]. CH;Cl;, respectively. The complexes1 and 2 react with phosphite donor ligands P（OMe）;to give [PhCl;SnM（Cl）(CO);-{P（OMe）;};]. All complexes have been characterized by elemental analysis, IRand;HNMR spectroscopies. Here we report the preliminary results of this work.展开更多
The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ...The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.展开更多
Catalytic polymerization of acetylene in the presence of n5-C5H5-M-(CO)3 R (M=Mo,W;R=CH3-,C2H5-) has been studied.The results show that these complexes possess catalytic activities for the polymerization and copolymer...Catalytic polymerization of acetylene in the presence of n5-C5H5-M-(CO)3 R (M=Mo,W;R=CH3-,C2H5-) has been studied.The results show that these complexes possess catalytic activities for the polymerization and copolymerization of monosubstituted acetylene.The catalytic mechanism has been preliminarily discussed.It is suggested that the active species be metal-car-bene.In our previous publications we reported the synthesis of some new Fischer's molybdenum and tungsten-carbene complexes and catalytic activity for alkyne polymerization.The results show that the activity of Fischer's molybdenum-carbene is higher than that of tungsten.The catalytic polymerization of alkyne by M-σ-c bond-containing complexes of molybdenum and tungsten has not been reported yet in literature.Therefore,four M-σ-C bondontaining complexes of molybdenum and tungsten were synthesized by using the method reported in the literature,and catalyst polymerization of alkyne by these complexes was examined.展开更多
A hexamolybdenum complex, [Et_4N]_2[Mo_6O_(19)H_4] crystal, with pentavalent and hexavalent molybdenum has been obtained in the solution of DMF and CH_3OH as organic solvents using MoCl_5 as a starting material. The c...A hexamolybdenum complex, [Et_4N]_2[Mo_6O_(19)H_4] crystal, with pentavalent and hexavalent molybdenum has been obtained in the solution of DMF and CH_3OH as organic solvents using MoCl_5 as a starting material. The crystallographic parameters obtained by X-ray diffraction analysis are: crthorhombic, a=10. 757(3), b=10. 763(2), c=14. 238(4)A, =1648. 9A^3; Z=2; space group Pnnm; final R=0. 047; final Rw=0. 051^(**)展开更多
The title complex, was pre-pared by using (NH4)2MoS4 as a starting material. X-ray crystal structural analysis ofthe complex gave the following parameters: In this complex, weak bond-ing of Cl- to three axial sulfur ...The title complex, was pre-pared by using (NH4)2MoS4 as a starting material. X-ray crystal structural analysis ofthe complex gave the following parameters: In this complex, weak bond-ing of Cl- to three axial sulfur atoms was found with average distance of 2. 717 TheCl atom locates at a special position and is bonded weakly by two cluster cations, indi-cating the oxidation number of + 1/2 for the cluster cation.展开更多
The application of phenylfluorone (PF)-Mo(VI) complex as a spectroscopic probe is studied. In the presence of OP microemulsion at pH 3.04, PF-Mo(Ⅵ) complex combines protein rapidly to form a stable compound and the a...The application of phenylfluorone (PF)-Mo(VI) complex as a spectroscopic probe is studied. In the presence of OP microemulsion at pH 3.04, PF-Mo(Ⅵ) complex combines protein rapidly to form a stable compound and the absorbance at 527 nm is in proportion to the concentration of protein in the range 0-16 μg mL-1 for bovine serum albumin (BSA). OP microemuslion media is introduced into protein determination, it has increased markedly the sensitivity of the system. The molar absorption coefficient was 5.98×l06 L mol-1 cm-1 for BSA. The assay, with sensitivity, simplicity and tolerance to many foreign substances, is applied to the determination of protein in samples with satisfactory results. Moreover, the binding number of BSA with the complex, which is determined by molar ratio and slope ratio methods, is in good agreement.展开更多
Molybenum＇s effects when added in the γ phase of nickel-based superalloys were studied using the lattice Green＇s function multiscale method. The electronic structure of the dislocation-Mo complex was analyzed and h...Molybenum＇s effects when added in the γ phase of nickel-based superalloys were studied using the lattice Green＇s function multiscale method. The electronic structure of the dislocation-Mo complex was analyzed and hybridization was found to contribute to the strengthening. Moreover, by combining the interaction energies calculated from two scales, the yield stress was theoretically predicted at 0 K and finite temperature.展开更多
基金Financial supports from the Natural Science Foundation of Shandong Province(Y2000B09)Shandong Provincial Science and Technology Program(03C05)are gratefully acknowledged
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.
基金the Opening Subject of the State Key Laboratory of Powder Metallurgy of China (Nos. 200506123105A and 20070620090631B14)
文摘A facile EDTA （ethylene diamine tetraacetic acid） complexing technique has been successfully employed to prepare La2Mo2O9 nanoparticles. The as-synthesized products are characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, and Fourier transform infrared spectroscopy （FT-IR）. The results show that a homogeneous transparent gel can be obtained with EDTA as the organic complexing reagent under the pH value of 3.0. Further thermal decomposition of the as-synthesized transparent gel by increasing the temperature up to 600℃ for 3 h results in the formation of La2Mo2O9 nanoparticles with a crystal size of about 30 nm. Moreover, the nanoparticles tend to form micrometer-sized aggregates with a three-dimensional network structure, which shows promising applications in solid oxide fuel cells （SOFC）, catalysts and so on.
文摘The synthesis and characterization of two chiral fullerene complexes (+)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(RR))] 1 and (-)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(SS))] 2 were described. The CD spectra of 1 and 2 inthe visible range show weak Cotton effects, which are approximately of mirror image, indicatingthat the appended pineno-groups with opposite chirality in bipyridines can perturb the fullerenechromophores through the molybdenum centers and lead to induced CD effects.
文摘The solid state reaction of MoCl3. 3H2O with 8--hydroxylquinine givesthe title compound MoO2, (C9H6NO)2. The crystallographic data for C18,H12,N2O4.Mo=monoclinic, space group C2/c, a= 13. 357(4), b= 9. 434(2), c= 13. 540(5) A, β=109. 39(6)°, V= 1609 (2) A3, Z= 4, M.= 416. 24, D.= 1. 72 g/cm3, μ(MoKa) 8. 19 cm-l, F(000) = 832, R= 0. 049 and Rw= 0. 058 for 1118 observed refletions.The Mo atom is,coordinated by two N atoms and two O atoms from two 8-hydroxylquinine and other two terminal O atoms, forming octahedral coordination geometry.
文摘The 1H and 13C NMR spectra of the dinuclear complexes of molybdenum(VI) withethylenediaminetetraacetic acid ([Mo(VI)]2-EDTA) and 3,12-bis(carboxymethyl)-6.9-dioxa-3,12-diazatetra-decanedioic acid(tMo(VI)]2-EGTA) at various temperatures were measured. The solutionstructure of the two dinuclear complexes was determined and the possible exchange process of theisomers is suggested
基金Supported by THE NATIONAL SCIENCE FOUNDATION OF CHINA
文摘Abstract The complexes [M（CO）;（CH;CN）;]（M=Mo, W）react with an equimolar quantity ofPhSnCl;in dichloromethane at room tempreture to afford new heterobinuclearcomplexes [PhCl;SnM（Cl）(CO);（CH;CN）;] [M=Mo（1）; W（2）]. The complexes reactwith two equivalents of PR;R’（R=Ph, R’=Ph, Me; R=Cy, R’=H） to yield stablecomplexes [PhCl;SnM（Cl）(CO);（PR;R’）;]. Reaction of[PhCl;SnM（Cl）(CO);（CH;CN）;]with one equivalent of PPh;（CH;）nPPh;（n=I,2） or bulky phosphine ligands PBu;Clin dichloromethane at room tempreture to give [PhCl;SnMo（Cl）(CO);{PPh;（CH;）n-PPh;}] .CH;Cl;, [PhCl;SnMo（Cl）(CO);PBu;Cl]. CH;Cl;, respectively. The complexes1 and 2 react with phosphite donor ligands P（OMe）;to give [PhCl;SnM（Cl）(CO);-{P（OMe）;};]. All complexes have been characterized by elemental analysis, IRand;HNMR spectroscopies. Here we report the preliminary results of this work.
文摘The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.
文摘Catalytic polymerization of acetylene in the presence of n5-C5H5-M-(CO)3 R (M=Mo,W;R=CH3-,C2H5-) has been studied.The results show that these complexes possess catalytic activities for the polymerization and copolymerization of monosubstituted acetylene.The catalytic mechanism has been preliminarily discussed.It is suggested that the active species be metal-car-bene.In our previous publications we reported the synthesis of some new Fischer's molybdenum and tungsten-carbene complexes and catalytic activity for alkyne polymerization.The results show that the activity of Fischer's molybdenum-carbene is higher than that of tungsten.The catalytic polymerization of alkyne by M-σ-c bond-containing complexes of molybdenum and tungsten has not been reported yet in literature.Therefore,four M-σ-C bondontaining complexes of molybdenum and tungsten were synthesized by using the method reported in the literature,and catalyst polymerization of alkyne by these complexes was examined.
文摘A hexamolybdenum complex, [Et_4N]_2[Mo_6O_(19)H_4] crystal, with pentavalent and hexavalent molybdenum has been obtained in the solution of DMF and CH_3OH as organic solvents using MoCl_5 as a starting material. The crystallographic parameters obtained by X-ray diffraction analysis are: crthorhombic, a=10. 757(3), b=10. 763(2), c=14. 238(4)A, =1648. 9A^3; Z=2; space group Pnnm; final R=0. 047; final Rw=0. 051^(**)
文摘The title complex, was pre-pared by using (NH4)2MoS4 as a starting material. X-ray crystal structural analysis ofthe complex gave the following parameters: In this complex, weak bond-ing of Cl- to three axial sulfur atoms was found with average distance of 2. 717 TheCl atom locates at a special position and is bonded weakly by two cluster cations, indi-cating the oxidation number of + 1/2 for the cluster cation.
文摘The application of phenylfluorone (PF)-Mo(VI) complex as a spectroscopic probe is studied. In the presence of OP microemulsion at pH 3.04, PF-Mo(Ⅵ) complex combines protein rapidly to form a stable compound and the absorbance at 527 nm is in proportion to the concentration of protein in the range 0-16 μg mL-1 for bovine serum albumin (BSA). OP microemuslion media is introduced into protein determination, it has increased markedly the sensitivity of the system. The molar absorption coefficient was 5.98×l06 L mol-1 cm-1 for BSA. The assay, with sensitivity, simplicity and tolerance to many foreign substances, is applied to the determination of protein in samples with satisfactory results. Moreover, the binding number of BSA with the complex, which is determined by molar ratio and slope ratio methods, is in good agreement.
基金Project supported by Beijing Municipality Science&Technology Commission,China(Grant No.D161100002416001)
文摘Molybenum＇s effects when added in the γ phase of nickel-based superalloys were studied using the lattice Green＇s function multiscale method. The electronic structure of the dislocation-Mo complex was analyzed and hybridization was found to contribute to the strengthening. Moreover, by combining the interaction energies calculated from two scales, the yield stress was theoretically predicted at 0 K and finite temperature.
