The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs...The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs to the monoclinic space group P2_1/n with a=9. 908(2), b= 17, 873(2), c= 13/450(2) A , β= 90. 09(1 )°,V = 2381. 6 (7 ) A￣3 , D_c = 1. 359 g/cm￣3 , Z= 2. The structure was refined to R =0. 0427 for 2562 reflections. The anion of the title compound can be described as an oxalate ligand (C_2O4￣2 ) bridging two [MoCl_2O(OH)] units, which contain Mo(V)atoms.展开更多
A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a =...A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.展开更多
The interactions of oxygen with pre-reduced silver catalysts as well as theircatalytic properties for CO selective oxidation in H_2 after oxygen pre-treatment are studied inthis paper. It is found that the pretreatmen...The interactions of oxygen with pre-reduced silver catalysts as well as theircatalytic properties for CO selective oxidation in H_2 after oxygen pre-treatment are studied inthis paper. It is found that the pretreatment exerts a strong influence on the activity andselectivity of the silver catalyst. A drop in activity and selectivity is observed after treating apre-reduced catalyst with oxygen at low temperatures, whereas a converse result is obtained after anoxidizing treatment at high temperatures (T ≥ 350℃). O_2-TPD results show that surface oxygenspecies adsorbs on silver surface after the oxygen treatment at low temperatures. However,penetration of oxygen into the silver is enhanced by a high temperature treatment, meanwhile thesurface oxygen species disappear. No other silver species except metallic silver are observed on allthe catalysts by XRD, and the size of silver particle is not changed after the treatment withoxygen at low temperatures. The surface oxygen species formed by oxygen treatment can also beremoved by hydrogen reduction. The strongly-adsorbed surface oxygen species prohibit the adsorptionand diffusion of oxygen species in reaction gas on the surface of silver catalyst, causing thedecrease in CO oxidation activity, in other words, it is important to obtain a clean silver surfacefor increasing the catalyst activity in CO removal from H_2-rich feed gas. The differences inactivity and selectivity due to the oxygen pretreatment at different temperatures are discussed interms of the changes in the surface/subsurface oxygen species of the silver particles.展开更多
The title complex, C18H15N3NiO3, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group Cc with a = 10.939(2), b = 22.909(5), c = 6.907(1) ?, β = 11...The title complex, C18H15N3NiO3, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group Cc with a = 10.939(2), b = 22.909(5), c = 6.907(1) ?, β = 116.75(3)°, V = 1545.7(5) ?, Z = 4, Mr = 380.04, F(000) = 784, Dc = 1.633 g/cm3 and μ(MoKα) = 1.279 mm–1. The structure was refined to R = 0.0472 and wR = 0.0893 for 2571 observed reflections with I > 2σ(I). The absolute structure Flack parameter X is 0.01(2). In this crystal structure, strong face-to-face π-π stacking interactions between adjacent molecules lead to a one-dimensional chain structure.展开更多
The support materials of ruthenium-based catalysts for ammonia synthesis were preparedusing mixed solutions composed of magnesium nitrate, aluminum nitrate and calcium nitrate with acertain ratio. The catalysts suppor...The support materials of ruthenium-based catalysts for ammonia synthesis were preparedusing mixed solutions composed of magnesium nitrate, aluminum nitrate and calcium nitrate with acertain ratio. The catalysts supported on complex oxides were more active and the optimal activitytemperatures were lower than that supported on single oxide under the same conditions. Thecatalyst with Mg-Al complex oxide as support prepared by calcinating hydrotalcite-like compoundhad significantly higher activity, 38.42 mL NH3?h-1?g-1 at 673 K. The BET determination showedthat the Mg-Al complex oxide possessed large surface area, 140.95 m2?g-1, similar to γ-Al2O3.展开更多
The insertion of CS_2 into M--S bonds has been studied. CS_2 can be inserted intopart of a set of Cu--S or Ag--S bonds in polynuclear compounds, forming clusterswith thiolate (RS^-) and trithiocarbonate (RSCS_2^-) mix...The insertion of CS_2 into M--S bonds has been studied. CS_2 can be inserted intopart of a set of Cu--S or Ag--S bonds in polynuclear compounds, forming clusterswith thiolate (RS^-) and trithiocarbonate (RSCS_2^-) mixed ligands. This is anew way to prepare clusters with sulphur-containing ligands, In 1986, Chadha reportedthe first cluster complex Cu_8(S_2CSMe_2Et)_4(SCMe_2Et)_4 prepared by insertionof CS_2 into Cu--S bonds. In recent years, we have obtained several clusters展开更多
The title compound has been synthesized by the reaction of (Bu4N)2MoS4, CuCl and (C6H5CS2)(Bu4N) in DMF and recrystallized from DMF/ Et2O. The red black crystal belongs to the triclinic space group P1 with a = 12. 021...The title compound has been synthesized by the reaction of (Bu4N)2MoS4, CuCl and (C6H5CS2)(Bu4N) in DMF and recrystallized from DMF/ Et2O. The red black crystal belongs to the triclinic space group P1 with a = 12. 021 (6), b = 17.045(8), c=17. 136(7)(?) , α=110.05(3), β=108.64(4), γ=103.87 (4)°, V = 2873(3)(?)3, Dc=1. 321gcm-3, Z = 2. The structure was refined to R = 0. 065 for .4783 reflections. The anion of the title compound can be described as a MoS42- tetrahedron coordinated by two [Cu(C6H5CS2)] units with the three metal atoms lying on a line. The coordination number of each Cu atom is three.展开更多
The bonding capacities of tetranuclear early transition-metal clusters have been estimated based on the extended Huckel calculations.Using the Walsh diagram which shows orbital levels during the variation in geometry,...The bonding capacities of tetranuclear early transition-metal clusters have been estimated based on the extended Huckel calculations.Using the Walsh diagram which shows orbital levels during the variation in geometry,a method has been established to determine their stability which is described with three factors:the symmetry and geometrical size,the distribution of ligands,and the number of cluster core electrons(CCEs).The stabilities of many cluster compounds can be successfully explained.展开更多
The title compound (C20H30N4O6, Mr = 422.48) was synthesized and its crystal structure was determined by X-ray diffraction method. It crystallizes in the triclinic system, space group P with cell parameters: a = 8.330...The title compound (C20H30N4O6, Mr = 422.48) was synthesized and its crystal structure was determined by X-ray diffraction method. It crystallizes in the triclinic system, space group P with cell parameters: a = 8.330(2), b = 8.468(2), c = 16.017(3) ? ?= 97.30(3), ?= 92.33(3), ?= 103.94(3)? V = 1084.7(4) ?, Dc = 1.294 g/cm3, Z = 2, F(000) = 452 and ?= 0.096 mm-1. The structure was refined to R = 0.0483 for 3732 observed reflections with I > 2s(I) and wR = 0.1335 for 4828 unique reflections. The hydantoin rings are planar and the two ring planes of one molecule are paralleled to each other.展开更多
A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11....A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11.289(2), b = 12.071(2), c = 12.113(2) ?, α = 72.90(3), β = 83.76(3), γ = 65.60(3)°, V = 1436.7(5) ?3, Z = 2, Mr = 653.79, F(000) = 676, Dc = 1.511 g/cm3, μ(MoKα) = 1.660 mm?1, the final R = 0.0334 and wR = 0.0856 for 5047 observed reflections (I > 2σ(I)). The asymmetric unit comprises two half-molecules. The complex is a centrosymmetric dimmer in which each copper(II) is coordinated in the equatorial plane to the N-(salicylidene)-3- dimethylaminopropylamine ligand through the deprotonated phenolic oxygen atom as well as the nitrogen atoms of imine and amine. The fourth coordination site is occupied by the nitrogen atom of NCS?, while the axial one by the symmetrically related phenoxy oxygen of the other monomeric unit. The Cu(II)…Cu(II) average distance is 3.110(1) ?.展开更多
The title compound FCu (C2O4) (phen ) H2O)] H2O (phen=1, 10-phenanthroline) crystallizes in monoclinic system, space group P21/n with a = 8. 453 1639 observed reflections. The Cu(Ⅱ) atom is coordinated bytwo N atoms ...The title compound FCu (C2O4) (phen ) H2O)] H2O (phen=1, 10-phenanthroline) crystallizes in monoclinic system, space group P21/n with a = 8. 453 1639 observed reflections. The Cu(Ⅱ) atom is coordinated bytwo N atoms of phen, two O atoms of oxalate and one O atom of water, and in square-pyramidal environment. The molecules of the structure are joined to each other in thecrystal lattice by hydrogen bonds to yield a one-dimensional chain structure.展开更多
The structure of 3a-(4-chlorophenyl)-1, 5-diphenyl-3a, 4,5,11-te-trahydrq-1, 2, 4-oxadiazolino [5, 4-d][1, 5] benzothiazepine (C28H21N2OClS) has been determined. The compound crystallizes in triclinic space group P1 w...The structure of 3a-(4-chlorophenyl)-1, 5-diphenyl-3a, 4,5,11-te-trahydrq-1, 2, 4-oxadiazolino [5, 4-d][1, 5] benzothiazepine (C28H21N2OClS) has been determined. The compound crystallizes in triclinic space group P1 with two formula units in a cell of dimensions: a =11. 114(2), b = 11. 673(1), c=10. 435(1) (?), α=98. 42(1), β=118. 69(1),γ = 98. 64(1)° and V = 1136. 2(3)(?)3. The structure was solved by using direct methods and refined by full matrix least-squares. The final crystallographic discrepancy factor is 0. 058 for 2384 observed reflections. The molecular backbone is a tricyclic system : The seven-membered hetero ring in the center is in twisted-boat conformation, and is cis-fused to 1, 2, 4-oxadiazolino ring which is in an envelope form, together with the equilaterally adjoined benzene ring . The compound has a non-planar conjugation system.展开更多
A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7...A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7 % for methanol at 1 MPa and 523 K. The activity of this catalyst is much higher than that of NC 207 catalyst at the same reaction conditions. It was suggested that the multi-walled structure CNTs favored both the couple transfer of the proton and electron over the surface of the catalyst and the uptake of hydrogen which was favorable to methanol synthesis.展开更多
The electronic structures of several dinuclears and trinuclears of molybdenum containing thiolates complexes have been calculated by quantum chemistry SCC-DV-Xa method, and the reactivity of complexes has been analy...The electronic structures of several dinuclears and trinuclears of molybdenum containing thiolates complexes have been calculated by quantum chemistry SCC-DV-Xa method, and the reactivity of complexes has been analyzed in terms of the molecular orbital energy level diagrams, orbital characters and charge populations.展开更多
The crystal structures of 2-methyl-4-methoxy-phenyl [1,5] benzothiazepine (compound A, C_(17)H_(17)NOS, M_r = 283. 4 , D_c = 1. 27 g/cm3 ) and 1-methy1-3a-(4-methoxy-phenyl)-5-phenyl-3a, 4, 5, 11-tetrahydro-1, 2, 4-ox...The crystal structures of 2-methyl-4-methoxy-phenyl [1,5] benzothiazepine (compound A, C_(17)H_(17)NOS, M_r = 283. 4 , D_c = 1. 27 g/cm3 ) and 1-methy1-3a-(4-methoxy-phenyl)-5-phenyl-3a, 4, 5, 11-tetrahydro-1, 2, 4-oxadiazolino [1,5] benzothiazepine (compound B, C_(24)H_(22)N_2O_2S, M_r = 402. 5, D_c=1. 29 g/cm3) were determined using direct methods. The compounds crystallize in space groups P2_1/c and P1 , respectively , with cell dimensions a = 19. 218 (2) b= 6.2815(2), c= 12. 265(2) a,β= 93. 938(1)° , V= 1477. 2(3)A 3 , Z = for compound A and a= 10. 963(1), b= 11. 082 (1), c= 10. 076 (1)A a= 72. 38 (1),β=108.19(1), γ= 115. 16(1)°, V= 1031. 9(2)A 3, Z= 2 for compound B, the final R values are 0. 061 and 0. 057, respectively. The benzothiazepine ring in compound A is in a boat like conformation, while in compound B it assumes a twistboat conformation and the five-membered oxadiazolino ring cis-fused to it is in an envelope form due to the stability of whole system.展开更多
The title complex chloro(p-toluidine)[4-(p-tolyl)imino-2-pentanone-3-oximato]- palladium(Ⅱ), PdCl(p-CH3C6H4NH2)(p-CH3C6H4-iai), C19H22ClN3O2Pd, (p-CH3C6H4NH2 and p-CH3C6H4-iai- are p-toluidine and the anion of 4-(p-t...The title complex chloro(p-toluidine)[4-(p-tolyl)imino-2-pentanone-3-oximato]- palladium(Ⅱ), PdCl(p-CH3C6H4NH2)(p-CH3C6H4-iai), C19H22ClN3O2Pd, (p-CH3C6H4NH2 and p-CH3C6H4-iai- are p-toluidine and the anion of 4-(p-tolyl)imino-2-pentanone-3-oximato, respec- tively), crystallizes in the monoclinic system, space group C2/c with a = 26.082(5), b = 13.521(3), c = 12.578(3) ? b = 112.18(3), Mr = 466.25, V = 4108(2) 3, Dc = 1.508 g/cm3, F(000) = 1888, m(MoKa) = 1.051 mm-1, Z = 8, the final R = 0.0368 and wR = 0.0855 for 3243 observed reflections (I ≥ 2s(I)). The coordination environment around Pd is a distorted PdClN3 square-plane composed of imino- and oximo-nitrogen from the Schiff base ligand of p-CH3C6H4-iai-, and amino-nitrogen from p-toluidine and chlorine atom.展开更多
The efficient chiral Ru 3(CO) 12 systems were prepared in situ from Ru 3(CO) 12 and various chiral diimino-or diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hy...The efficient chiral Ru 3(CO) 12 systems were prepared in situ from Ru 3(CO) 12 and various chiral diimino-or diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu 3(CO) 11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru 3 framework.展开更多
X-ray photoelectron spectroscopy(XPS) and extended X-ray absorption fine structure(EXAFS) were used to characterize the structure of the mixture of molybdenum oxide and anatase calcined at 723 K. The results indicate ...X-ray photoelectron spectroscopy(XPS) and extended X-ray absorption fine structure(EXAFS) were used to characterize the structure of the mixture of molybdenum oxide and anatase calcined at 723 K. The results indicate that molybdenum oxide can disperse onto the surface of anatase(TiO 2) and the dispersion threshold is 11.2 mg in per gram of MoO 3 or 4.8 Mo atoms/nm 2 TiO 2. When the content of MoO 3 is below the dispersion threshold, MoO 3 species is in highly dispersed state interacting strongly with TiO 2 support and in discrete tetrahedral coordination, [MoO 4], on the surface of TiO 2. When the MoO 3 loading is above this value, MoO 3 exists in both dispersed phase and crystalline phase. MoO 3 in dispersed phase is still a discrete [MoO 4] tetrahedron; MoO 3 in crystal phase is in octahedral coordination.展开更多
b Laboratory Center, Fuzhou University, Fuzhou, Fujian 350002, China Three palladium(II) complexes with the isonitrosobenzoylacetoneimine (HIBI) ligand, Pd( p CH 3C 6H 4IBI) 2(1), Pd(C 6H 5IBI) 2(2) and ...b Laboratory Center, Fuzhou University, Fuzhou, Fujian 350002, China Three palladium(II) complexes with the isonitrosobenzoylacetoneimine (HIBI) ligand, Pd( p CH 3C 6H 4IBI) 2(1), Pd(C 6H 5IBI) 2(2) and Pd 2Cl 2(C 6H 5CH 2IBI) 2·CHCl 3(3), were prepared and characterized by IR, Raman and X ray diffraction studies. The geometries around the palladium atoms in the complexes 1 and 2 are distorted trans PdN 4 square planes, and the Schiff base ligands RIBI - are coordinated through their oximo nitrogen atoms and imino nitrogen atoms. The week Pd...H-C agostic interactions [Pd...H=0.2764 nm] complete the hexacoordinate environment around palladium in the complex 1. The octahedral deformation of the classical square planar environment of the Pd atom is due to the week Pd...O(1b) interactions [Pd-O(1b)=0.3157(9) nm] in the complex 2. The complex 3 is a first example of binuclear complex with isonitrosoketoimine ligands, in which one of oximo groups is coordinated through oximo nitrogen and oximo oxygen atoms.展开更多
文摘The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs to the monoclinic space group P2_1/n with a=9. 908(2), b= 17, 873(2), c= 13/450(2) A , β= 90. 09(1 )°,V = 2381. 6 (7 ) A￣3 , D_c = 1. 359 g/cm￣3 , Z= 2. The structure was refined to R =0. 0427 for 2562 reflections. The anion of the title compound can be described as an oxalate ligand (C_2O4￣2 ) bridging two [MoCl_2O(OH)] units, which contain Mo(V)atoms.
文摘A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.
文摘The interactions of oxygen with pre-reduced silver catalysts as well as theircatalytic properties for CO selective oxidation in H_2 after oxygen pre-treatment are studied inthis paper. It is found that the pretreatment exerts a strong influence on the activity andselectivity of the silver catalyst. A drop in activity and selectivity is observed after treating apre-reduced catalyst with oxygen at low temperatures, whereas a converse result is obtained after anoxidizing treatment at high temperatures (T ≥ 350℃). O_2-TPD results show that surface oxygenspecies adsorbs on silver surface after the oxygen treatment at low temperatures. However,penetration of oxygen into the silver is enhanced by a high temperature treatment, meanwhile thesurface oxygen species disappear. No other silver species except metallic silver are observed on allthe catalysts by XRD, and the size of silver particle is not changed after the treatment withoxygen at low temperatures. The surface oxygen species formed by oxygen treatment can also beremoved by hydrogen reduction. The strongly-adsorbed surface oxygen species prohibit the adsorptionand diffusion of oxygen species in reaction gas on the surface of silver catalyst, causing thedecrease in CO oxidation activity, in other words, it is important to obtain a clean silver surfacefor increasing the catalyst activity in CO removal from H_2-rich feed gas. The differences inactivity and selectivity due to the oxygen pretreatment at different temperatures are discussed interms of the changes in the surface/subsurface oxygen species of the silver particles.
基金The project was supported by the Education Department of Zhejiang Province (20030710)
文摘The title complex, C18H15N3NiO3, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group Cc with a = 10.939(2), b = 22.909(5), c = 6.907(1) ?, β = 116.75(3)°, V = 1545.7(5) ?, Z = 4, Mr = 380.04, F(000) = 784, Dc = 1.633 g/cm3 and μ(MoKα) = 1.279 mm–1. The structure was refined to R = 0.0472 and wR = 0.0893 for 2571 observed reflections with I > 2σ(I). The absolute structure Flack parameter X is 0.01(2). In this crystal structure, strong face-to-face π-π stacking interactions between adjacent molecules lead to a one-dimensional chain structure.
基金This work was supported by the NNSF of China(20273053,20023001 and 29933040)the 973 Programming(001CB108906)the NSF of Fujian province(E0310001).
文摘The support materials of ruthenium-based catalysts for ammonia synthesis were preparedusing mixed solutions composed of magnesium nitrate, aluminum nitrate and calcium nitrate with acertain ratio. The catalysts supported on complex oxides were more active and the optimal activitytemperatures were lower than that supported on single oxide under the same conditions. Thecatalyst with Mg-Al complex oxide as support prepared by calcinating hydrotalcite-like compoundhad significantly higher activity, 38.42 mL NH3?h-1?g-1 at 673 K. The BET determination showedthat the Mg-Al complex oxide possessed large surface area, 140.95 m2?g-1, similar to γ-Al2O3.
文摘The insertion of CS_2 into M--S bonds has been studied. CS_2 can be inserted intopart of a set of Cu--S or Ag--S bonds in polynuclear compounds, forming clusterswith thiolate (RS^-) and trithiocarbonate (RSCS_2^-) mixed ligands. This is anew way to prepare clusters with sulphur-containing ligands, In 1986, Chadha reportedthe first cluster complex Cu_8(S_2CSMe_2Et)_4(SCMe_2Et)_4 prepared by insertionof CS_2 into Cu--S bonds. In recent years, we have obtained several clusters
文摘The title compound has been synthesized by the reaction of (Bu4N)2MoS4, CuCl and (C6H5CS2)(Bu4N) in DMF and recrystallized from DMF/ Et2O. The red black crystal belongs to the triclinic space group P1 with a = 12. 021 (6), b = 17.045(8), c=17. 136(7)(?) , α=110.05(3), β=108.64(4), γ=103.87 (4)°, V = 2873(3)(?)3, Dc=1. 321gcm-3, Z = 2. The structure was refined to R = 0. 065 for .4783 reflections. The anion of the title compound can be described as a MoS42- tetrahedron coordinated by two [Cu(C6H5CS2)] units with the three metal atoms lying on a line. The coordination number of each Cu atom is three.
基金Project supported by the National Natural Science Foundation of China
文摘The bonding capacities of tetranuclear early transition-metal clusters have been estimated based on the extended Huckel calculations.Using the Walsh diagram which shows orbital levels during the variation in geometry,a method has been established to determine their stability which is described with three factors:the symmetry and geometrical size,the distribution of ligands,and the number of cluster core electrons(CCEs).The stabilities of many cluster compounds can be successfully explained.
基金This project was supported by the National Natural Science Foundation of China (No 39870983)
文摘The title compound (C20H30N4O6, Mr = 422.48) was synthesized and its crystal structure was determined by X-ray diffraction method. It crystallizes in the triclinic system, space group P with cell parameters: a = 8.330(2), b = 8.468(2), c = 16.017(3) ? ?= 97.30(3), ?= 92.33(3), ?= 103.94(3)? V = 1084.7(4) ?, Dc = 1.294 g/cm3, Z = 2, F(000) = 452 and ?= 0.096 mm-1. The structure was refined to R = 0.0483 for 3732 observed reflections with I > 2s(I) and wR = 0.1335 for 4828 unique reflections. The hydantoin rings are planar and the two ring planes of one molecule are paralleled to each other.
文摘A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11.289(2), b = 12.071(2), c = 12.113(2) ?, α = 72.90(3), β = 83.76(3), γ = 65.60(3)°, V = 1436.7(5) ?3, Z = 2, Mr = 653.79, F(000) = 676, Dc = 1.511 g/cm3, μ(MoKα) = 1.660 mm?1, the final R = 0.0334 and wR = 0.0856 for 5047 observed reflections (I > 2σ(I)). The asymmetric unit comprises two half-molecules. The complex is a centrosymmetric dimmer in which each copper(II) is coordinated in the equatorial plane to the N-(salicylidene)-3- dimethylaminopropylamine ligand through the deprotonated phenolic oxygen atom as well as the nitrogen atoms of imine and amine. The fourth coordination site is occupied by the nitrogen atom of NCS?, while the axial one by the symmetrically related phenoxy oxygen of the other monomeric unit. The Cu(II)…Cu(II) average distance is 3.110(1) ?.
文摘The title compound FCu (C2O4) (phen ) H2O)] H2O (phen=1, 10-phenanthroline) crystallizes in monoclinic system, space group P21/n with a = 8. 453 1639 observed reflections. The Cu(Ⅱ) atom is coordinated bytwo N atoms of phen, two O atoms of oxalate and one O atom of water, and in square-pyramidal environment. The molecules of the structure are joined to each other in thecrystal lattice by hydrogen bonds to yield a one-dimensional chain structure.
文摘The structure of 3a-(4-chlorophenyl)-1, 5-diphenyl-3a, 4,5,11-te-trahydrq-1, 2, 4-oxadiazolino [5, 4-d][1, 5] benzothiazepine (C28H21N2OClS) has been determined. The compound crystallizes in triclinic space group P1 with two formula units in a cell of dimensions: a =11. 114(2), b = 11. 673(1), c=10. 435(1) (?), α=98. 42(1), β=118. 69(1),γ = 98. 64(1)° and V = 1136. 2(3)(?)3. The structure was solved by using direct methods and refined by full matrix least-squares. The final crystallographic discrepancy factor is 0. 058 for 2384 observed reflections. The molecular backbone is a tricyclic system : The seven-membered hetero ring in the center is in twisted-boat conformation, and is cis-fused to 1, 2, 4-oxadiazolino ring which is in an envelope form, together with the equilaterally adjoined benzene ring . The compound has a non-planar conjugation system.
基金supportd by the NNSF of China(#29773037)the NSF of Fujian province(#E9910001 and#E0010006).|
文摘A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7 % for methanol at 1 MPa and 523 K. The activity of this catalyst is much higher than that of NC 207 catalyst at the same reaction conditions. It was suggested that the multi-walled structure CNTs favored both the couple transfer of the proton and electron over the surface of the catalyst and the uptake of hydrogen which was favorable to methanol synthesis.
文摘The electronic structures of several dinuclears and trinuclears of molybdenum containing thiolates complexes have been calculated by quantum chemistry SCC-DV-Xa method, and the reactivity of complexes has been analyzed in terms of the molecular orbital energy level diagrams, orbital characters and charge populations.
文摘The crystal structures of 2-methyl-4-methoxy-phenyl [1,5] benzothiazepine (compound A, C_(17)H_(17)NOS, M_r = 283. 4 , D_c = 1. 27 g/cm3 ) and 1-methy1-3a-(4-methoxy-phenyl)-5-phenyl-3a, 4, 5, 11-tetrahydro-1, 2, 4-oxadiazolino [1,5] benzothiazepine (compound B, C_(24)H_(22)N_2O_2S, M_r = 402. 5, D_c=1. 29 g/cm3) were determined using direct methods. The compounds crystallize in space groups P2_1/c and P1 , respectively , with cell dimensions a = 19. 218 (2) b= 6.2815(2), c= 12. 265(2) a,β= 93. 938(1)° , V= 1477. 2(3)A 3 , Z = for compound A and a= 10. 963(1), b= 11. 082 (1), c= 10. 076 (1)A a= 72. 38 (1),β=108.19(1), γ= 115. 16(1)°, V= 1031. 9(2)A 3, Z= 2 for compound B, the final R values are 0. 061 and 0. 057, respectively. The benzothiazepine ring in compound A is in a boat like conformation, while in compound B it assumes a twistboat conformation and the five-membered oxadiazolino ring cis-fused to it is in an envelope form due to the stability of whole system.
基金Supported by the Natural Science Foundation of Fujian province (No. E0110010)
文摘The title complex chloro(p-toluidine)[4-(p-tolyl)imino-2-pentanone-3-oximato]- palladium(Ⅱ), PdCl(p-CH3C6H4NH2)(p-CH3C6H4-iai), C19H22ClN3O2Pd, (p-CH3C6H4NH2 and p-CH3C6H4-iai- are p-toluidine and the anion of 4-(p-tolyl)imino-2-pentanone-3-oximato, respec- tively), crystallizes in the monoclinic system, space group C2/c with a = 26.082(5), b = 13.521(3), c = 12.578(3) ? b = 112.18(3), Mr = 466.25, V = 4108(2) 3, Dc = 1.508 g/cm3, F(000) = 1888, m(MoKa) = 1.051 mm-1, Z = 8, the final R = 0.0368 and wR = 0.0855 for 3243 observed reflections (I ≥ 2s(I)). The coordination environment around Pd is a distorted PdClN3 square-plane composed of imino- and oximo-nitrogen from the Schiff base ligand of p-CH3C6H4-iai-, and amino-nitrogen from p-toluidine and chlorine atom.
基金Supported by the National Natural Science Foundation of China(No.2 0 0 730 34,2 0 3730 5 6,2 0 1710 37),Fujian Provinceand Technology Comm ission(No.2 0 0 2 F0 16 ) and Xiamen Science and Technology Com mission(No.35 0 2 Z2 0 0 2 10 4 4 )
文摘The efficient chiral Ru 3(CO) 12 systems were prepared in situ from Ru 3(CO) 12 and various chiral diimino-or diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu 3(CO) 11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru 3 framework.
基金the National Natural Science Foundation of China(No.2 97330 80 ) and the Major State Basic ResearchDevelopment Program(No.G2 0 0 0 0 775 0 3)
文摘X-ray photoelectron spectroscopy(XPS) and extended X-ray absorption fine structure(EXAFS) were used to characterize the structure of the mixture of molybdenum oxide and anatase calcined at 723 K. The results indicate that molybdenum oxide can disperse onto the surface of anatase(TiO 2) and the dispersion threshold is 11.2 mg in per gram of MoO 3 or 4.8 Mo atoms/nm 2 TiO 2. When the content of MoO 3 is below the dispersion threshold, MoO 3 species is in highly dispersed state interacting strongly with TiO 2 support and in discrete tetrahedral coordination, [MoO 4], on the surface of TiO 2. When the MoO 3 loading is above this value, MoO 3 exists in both dispersed phase and crystalline phase. MoO 3 in dispersed phase is still a discrete [MoO 4] tetrahedron; MoO 3 in crystal phase is in octahedral coordination.
基金theEducationCommissionofZhejiangProvince (No .2 0 0 0 0 16 8)
文摘b Laboratory Center, Fuzhou University, Fuzhou, Fujian 350002, China Three palladium(II) complexes with the isonitrosobenzoylacetoneimine (HIBI) ligand, Pd( p CH 3C 6H 4IBI) 2(1), Pd(C 6H 5IBI) 2(2) and Pd 2Cl 2(C 6H 5CH 2IBI) 2·CHCl 3(3), were prepared and characterized by IR, Raman and X ray diffraction studies. The geometries around the palladium atoms in the complexes 1 and 2 are distorted trans PdN 4 square planes, and the Schiff base ligands RIBI - are coordinated through their oximo nitrogen atoms and imino nitrogen atoms. The week Pd...H-C agostic interactions [Pd...H=0.2764 nm] complete the hexacoordinate environment around palladium in the complex 1. The octahedral deformation of the classical square planar environment of the Pd atom is due to the week Pd...O(1b) interactions [Pd-O(1b)=0.3157(9) nm] in the complex 2. The complex 3 is a first example of binuclear complex with isonitrosoketoimine ligands, in which one of oximo groups is coordinated through oximo nitrogen and oximo oxygen atoms.
