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
The crystal and molecular structures of molybdenum complex, Mo [ o- NHCOCH3- m-NO2C6H3COOH]2O2Cl2.PhCl are reported. The crystal belongs to space group Cc of monoclinic system with unit cell parameters:α= 11. 214 (3)...The crystal and molecular structures of molybdenum complex, Mo [ o- NHCOCH3- m-NO2C6H3COOH]2O2Cl2.PhCl are reported. The crystal belongs to space group Cc of monoclinic system with unit cell parameters:α= 11. 214 (3) A .b= 19. 544 (4 ) A . c = 14. 091 (6) A .β=94.06(3)°,V'=3080.3 A3 and Z=4. The structure was refined to R=0. 061.The coordination number for the Mo atom Is six. The coordination polyhedron formed by four O atoms and two Cl atoms around the Mo atom is a distorted octahedron. Four O atoms and one Mo atom construct a plane. Two benzyl planes in coordinate groups and the benzyl plane of solvent are almost parallel. The quantum-chemical calculations were carried out. There are hydrogen bonds in the Complex. The EHMO calculations and the existence of hydrogen bonds prove that the O atoms are stronger coordinated atoms in the carbonyls than in the carboxyls.展开更多
The title complex (enH2){NH4[Co(en)3][Mo2O7(C2O4)]}22H2O (C18H70Co2Mo4- N16O24, Mr = 1396.52) was obtained under hydrothermal conditions and its crystal structure has been determined by single-crystal X-ray diffractio...The title complex (enH2){NH4[Co(en)3][Mo2O7(C2O4)]}22H2O (C18H70Co2Mo4- N16O24, Mr = 1396.52) was obtained under hydrothermal conditions and its crystal structure has been determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 17.8023(8), b = 7.7527(4), c = 16.9781(4) ? b = 103.878(7), V = 2274.8(2) 3, Dc = 2.039 g/cm3, Z = 2, m(MoKa) = 1.878 mm-1 and F(000) = 1408. The final R = 0.0410 and wR = 0.1070 for 4065 observed reflections with I≥2s(I). The crystal structure is composed of bi- nuclear [Mo2O7(C2O4)]4- anions, complex [Co(en)3]2+ cations, protonated ethylenediamine cations, ammonium cations and crystal water molecules, which are held together into a three-dimensional network via hydrogen-bonding interactions. The binuclear structure of [Mo2O7(C2O4)]4- consist of one MoO4 and one MoO6 octahedra through sharing a bridging oxygen atom, where the oxalate ligand acts as a bidentate ligand coordinating to the octahedral molybdenum atom though two deprotonated corboxylate groups.展开更多
Two complexes [H3N（CH2）2NH2]2[MoO2（C10H8O2）2] （1） and （C7H10N2）2- [MoO2（C10H8O2）2] （2） were obtained at nearly the same reaction condition and characterized by IR, 1H and 13C NMR and single-crystal X-ray d...Two complexes [H3N（CH2）2NH2]2[MoO2（C10H8O2）2] （1） and （C7H10N2）2- [MoO2（C10H8O2）2] （2） were obtained at nearly the same reaction condition and characterized by IR, 1H and 13C NMR and single-crystal X-ray diffraction. Both of the complexes possess complex anion [MoO2（C10H8O2）2]2- which shows a pseudo-octahedrally coordinated fashion. In complex 1, ethyldiamine presents just as a cation. However, in complex 2, ethyldiamine combines with the acetyl acetone as a byproduct which is confirmed by NMR.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
C<sub>14</sub>H<sub>9</sub>NO<sub>2</sub>S<sub>2</sub>Mo,Mr=383.29,triclinic,space group P1,a=11.658（4）,b=16.218（8）,c=7.895（3）,a=97.58（4）,β=106.04（3）,γ=85.62...C<sub>14</sub>H<sub>9</sub>NO<sub>2</sub>S<sub>2</sub>Mo,Mr=383.29,triclinic,space group P1,a=11.658（4）,b=16.218（8）,c=7.895（3）,a=97.58（4）,β=106.04（3）,γ=85.62（3）°,V=1421（2）,Z=4,D<sub>c</sub>=1.79 g/cm￣3,μ=11.81 cm￣（-1）.F（000）=760.Refinement converged to R=0.049 and Rω=0.058 for 3153 independent observed reflections.The compound is a mononuclear molybdenum complex containing benzothiazole-2-thiolato ligand.The molybdenum atom is coordinated by the two carbonyl carbon atoms,tlie cyclopentadienyl carbon atoms,and the nitrogen atom and sulfur atom of benzothiazole-2-thiolate.The coordination polyhedron may be described as a trapezoidal pyramid with the Cp ring centroid as a top.展开更多
The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0....The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.展开更多
The deprotonated derivative pyridine-2-thiolato （PyS<sup>-</sup>） of pyridine-2-thione （PySH）is a potentially amibidentate or multi-functional donor which coordinates toward transitionmetals with eithe...The deprotonated derivative pyridine-2-thiolato （PyS<sup>-</sup>） of pyridine-2-thione （PySH）is a potentially amibidentate or multi-functional donor which coordinates toward transitionmetals with either the exocyclic S or heterocyclic N atom or both atoms to form differentcoordination modes. We have recently reported the synthesis and crystal structure ofthe first dinuclear molybdenum complex with doubly-bridging PyS ligands [Mo<sub>2</sub>（CO）<sub>4</sub>（μ-PyS）<sub>2</sub>（PPh<sub>3</sub>）<sub>2</sub>]which was obtained from the reaction of [Mo（CO）<sub>3</sub>（CH<sub>3</sub>CN）<sub>3</sub>]展开更多
The complex (Bu4N) 2 [Mo2O5 (mp)2] was synthesized by the reactionof (Bu4N)2[Mo8O26] with H2mp (H2mp=o-mercaptophenol) in methanol. The molecular formula is C44H80Mo2N2O7S2, M.=1005.10. The complex is crystallized in ...The complex (Bu4N) 2 [Mo2O5 (mp)2] was synthesized by the reactionof (Bu4N)2[Mo8O26] with H2mp (H2mp=o-mercaptophenol) in methanol. The molecular formula is C44H80Mo2N2O7S2, M.=1005.10. The complex is crystallized in monoclinic, space group P21/n with unit cell parameters, a = 17. 829 (2) A, b= 13. 759 (2 )A,c= 21. 974(2) A, g=105. 386(8)°, V= 5197. 4(1) , Dc= 1. 285 g/cm3, Z=4,λ(MoKa) =0. 71073 , μ=0. 607 mm-1,F(000) = 2120, final R=0.0348 and wR=0. 0741 for 4912 independent observed reflections (FM>4σ(Fo) ). Two MoO5S units inthe complex molecule exhibits the con facial distorted bioctahedral geometry and possesses an approximate C2 symmetry.展开更多
A dimolybdenum complex [Mo（S<sub>2</sub>CNEt<sub>2</sub>）<sub>4</sub>] （MoCl<sub>6</sub>） has been synthesized with MoCl<sub>5</sub>. In this note, we re...A dimolybdenum complex [Mo（S<sub>2</sub>CNEt<sub>2</sub>）<sub>4</sub>] （MoCl<sub>6</sub>） has been synthesized with MoCl<sub>5</sub>. In this note, we report the synthesis and structure of a new trimolybdenum complex.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
A di-molybdenum carbonyl compound containing thiolate and dithiocarbamate ligands, [Bu4N][（CO）4Mo（μ-SC6H5）2Mo（C5H10dtc）（CO）2] 1 （CsH10dtc = S2CNC5H10）, has been prepared by reaction of [Mo2（SC6H5）2（CO）8...A di-molybdenum carbonyl compound containing thiolate and dithiocarbamate ligands, [Bu4N][（CO）4Mo（μ-SC6H5）2Mo（C5H10dtc）（CO）2] 1 （CsH10dtc = S2CNC5H10）, has been prepared by reaction of [Mo2（SC6H5）2（CO）8] with C5H10dtcNa and [NBu4]Br in acetone. It crystallizes in monoclinic, space group P21/n with a = 13.162（3）, b = 17.466（2）, c = 20.453（4） A,β= 100.77（1）°, Z = 4, V= 4619（2）A^3, C40H56Mo2N2O6S4, Mr = 980.95, De= 1.389 g/cm^3,μ = 7.66 cm^-1, F（000） = 1988 and R = 0.0746 for 5161 observed reflections with I 〉 2σ（I）. The complex contains a [Mo2S2]^2- planar core in which one Mo atom is chelated by a C5H10dtc ligand, leading to different coordination environments of the two Mo atoms. 95Mo NMR measurement indicates that the two Mo atoms are in different oxidation states.展开更多
The complex MoO2(C7H7O3)2 has been prepared by the reaction of 3-hydroxy- 2-ethyl-4-pyranone with (NH4)6Mo7O244H2O. The single-crystal X-ray study shows that the coordination sphere about the molybdenum atom in the co...The complex MoO2(C7H7O3)2 has been prepared by the reaction of 3-hydroxy- 2-ethyl-4-pyranone with (NH4)6Mo7O244H2O. The single-crystal X-ray study shows that the coordination sphere about the molybdenum atom in the complex consists of six oxygen atoms arranged in a distorted octahedral geometry with the dioxo ligands in cis positions. The crystal is of monoclinic, space group P21/c with a = 8.3968(2), b = 12.7534(4), c = 14.5443(4) ? b = 96.277(1), V = 1548.18(7) ?, Z = 4, C14H14O8Mo, Mr = 406.19, Dc = 1.743g/cm3, m = 0.886mm-1, F(000) = 816, R = 0.0444 and wR = 0.1091 for 2336 observed reflections with I>2s(I). The average Mo=O bond length is 1.695(4) ? The two ketonic oxygen atoms of the pyranone moieties are trans to the oxo ligands and the hydroxy oxygen atoms are trans to each other. The average MoO bond lengths are 2.248(4) ?for the ketone oxygens and 2.005(3) ?for the hydroxy oxygens. The average ligand bite angle of OMoO is 75.2(2) and the bond angle between two Mo=O is 105.1(2). The dihedral angle is 79.16(2)?between two chelate ring planes.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The crystal and molecular structures of molybdenum complex, Mo [ o- NHCOCH3- m-NO2C6H3COOH]2O2Cl2.PhCl are reported. The crystal belongs to space group Cc of monoclinic system with unit cell parameters:α= 11. 214 (3) A .b= 19. 544 (4 ) A . c = 14. 091 (6) A .β=94.06(3)°,V'=3080.3 A3 and Z=4. The structure was refined to R=0. 061.The coordination number for the Mo atom Is six. The coordination polyhedron formed by four O atoms and two Cl atoms around the Mo atom is a distorted octahedron. Four O atoms and one Mo atom construct a plane. Two benzyl planes in coordinate groups and the benzyl plane of solvent are almost parallel. The quantum-chemical calculations were carried out. There are hydrogen bonds in the Complex. The EHMO calculations and the existence of hydrogen bonds prove that the O atoms are stronger coordinated atoms in the carbonyls than in the carboxyls.
基金the Natural Science Foundation of Fujian province
文摘The title complex (enH2){NH4[Co(en)3][Mo2O7(C2O4)]}22H2O (C18H70Co2Mo4- N16O24, Mr = 1396.52) was obtained under hydrothermal conditions and its crystal structure has been determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 17.8023(8), b = 7.7527(4), c = 16.9781(4) ? b = 103.878(7), V = 2274.8(2) 3, Dc = 2.039 g/cm3, Z = 2, m(MoKa) = 1.878 mm-1 and F(000) = 1408. The final R = 0.0410 and wR = 0.1070 for 4065 observed reflections with I≥2s(I). The crystal structure is composed of bi- nuclear [Mo2O7(C2O4)]4- anions, complex [Co(en)3]2+ cations, protonated ethylenediamine cations, ammonium cations and crystal water molecules, which are held together into a three-dimensional network via hydrogen-bonding interactions. The binuclear structure of [Mo2O7(C2O4)]4- consist of one MoO4 and one MoO6 octahedra through sharing a bridging oxygen atom, where the oxalate ligand acts as a bidentate ligand coordinating to the octahedral molybdenum atom though two deprotonated corboxylate groups.
基金Supported by the National Natural Science Foundation of China (20871085)Beijing Natural Science Foundation (2092009)
文摘Two complexes [H3N（CH2）2NH2]2[MoO2（C10H8O2）2] （1） and （C7H10N2）2- [MoO2（C10H8O2）2] （2） were obtained at nearly the same reaction condition and characterized by IR, 1H and 13C NMR and single-crystal X-ray diffraction. Both of the complexes possess complex anion [MoO2（C10H8O2）2]2- which shows a pseudo-octahedrally coordinated fashion. In complex 1, ethyldiamine presents just as a cation. However, in complex 2, ethyldiamine combines with the acetyl acetone as a byproduct which is confirmed by NMR.
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C<sub>14</sub>H<sub>9</sub>NO<sub>2</sub>S<sub>2</sub>Mo,Mr=383.29,triclinic,space group P1,a=11.658（4）,b=16.218（8）,c=7.895（3）,a=97.58（4）,β=106.04（3）,γ=85.62（3）°,V=1421（2）,Z=4,D<sub>c</sub>=1.79 g/cm￣3,μ=11.81 cm￣（-1）.F（000）=760.Refinement converged to R=0.049 and Rω=0.058 for 3153 independent observed reflections.The compound is a mononuclear molybdenum complex containing benzothiazole-2-thiolato ligand.The molybdenum atom is coordinated by the two carbonyl carbon atoms,tlie cyclopentadienyl carbon atoms,and the nitrogen atom and sulfur atom of benzothiazole-2-thiolate.The coordination polyhedron may be described as a trapezoidal pyramid with the Cp ring centroid as a top.
基金supported by the National Natural Science Foundation of China(21173100 and 21320102001)~~
文摘The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.
文摘The deprotonated derivative pyridine-2-thiolato （PyS<sup>-</sup>） of pyridine-2-thione （PySH）is a potentially amibidentate or multi-functional donor which coordinates toward transitionmetals with either the exocyclic S or heterocyclic N atom or both atoms to form differentcoordination modes. We have recently reported the synthesis and crystal structure ofthe first dinuclear molybdenum complex with doubly-bridging PyS ligands [Mo<sub>2</sub>（CO）<sub>4</sub>（μ-PyS）<sub>2</sub>（PPh<sub>3</sub>）<sub>2</sub>]which was obtained from the reaction of [Mo（CO）<sub>3</sub>（CH<sub>3</sub>CN）<sub>3</sub>]
文摘The complex (Bu4N) 2 [Mo2O5 (mp)2] was synthesized by the reactionof (Bu4N)2[Mo8O26] with H2mp (H2mp=o-mercaptophenol) in methanol. The molecular formula is C44H80Mo2N2O7S2, M.=1005.10. The complex is crystallized in monoclinic, space group P21/n with unit cell parameters, a = 17. 829 (2) A, b= 13. 759 (2 )A,c= 21. 974(2) A, g=105. 386(8)°, V= 5197. 4(1) , Dc= 1. 285 g/cm3, Z=4,λ(MoKa) =0. 71073 , μ=0. 607 mm-1,F(000) = 2120, final R=0.0348 and wR=0. 0741 for 4912 independent observed reflections (FM>4σ(Fo) ). Two MoO5S units inthe complex molecule exhibits the con facial distorted bioctahedral geometry and possesses an approximate C2 symmetry.
文摘A dimolybdenum complex [Mo（S<sub>2</sub>CNEt<sub>2</sub>）<sub>4</sub>] （MoCl<sub>6</sub>） has been synthesized with MoCl<sub>5</sub>. In this note, we report the synthesis and structure of a new trimolybdenum complex.
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A di-molybdenum carbonyl compound containing thiolate and dithiocarbamate ligands, [Bu4N][（CO）4Mo（μ-SC6H5）2Mo（C5H10dtc）（CO）2] 1 （CsH10dtc = S2CNC5H10）, has been prepared by reaction of [Mo2（SC6H5）2（CO）8] with C5H10dtcNa and [NBu4]Br in acetone. It crystallizes in monoclinic, space group P21/n with a = 13.162（3）, b = 17.466（2）, c = 20.453（4） A,β= 100.77（1）°, Z = 4, V= 4619（2）A^3, C40H56Mo2N2O6S4, Mr = 980.95, De= 1.389 g/cm^3,μ = 7.66 cm^-1, F（000） = 1988 and R = 0.0746 for 5161 observed reflections with I 〉 2σ（I）. The complex contains a [Mo2S2]^2- planar core in which one Mo atom is chelated by a C5H10dtc ligand, leading to different coordination environments of the two Mo atoms. 95Mo NMR measurement indicates that the two Mo atoms are in different oxidation states.
基金the Natural Science Foundation of Jiangsu Education Department (No. 02KJB15007)
文摘The complex MoO2(C7H7O3)2 has been prepared by the reaction of 3-hydroxy- 2-ethyl-4-pyranone with (NH4)6Mo7O244H2O. The single-crystal X-ray study shows that the coordination sphere about the molybdenum atom in the complex consists of six oxygen atoms arranged in a distorted octahedral geometry with the dioxo ligands in cis positions. The crystal is of monoclinic, space group P21/c with a = 8.3968(2), b = 12.7534(4), c = 14.5443(4) ? b = 96.277(1), V = 1548.18(7) ?, Z = 4, C14H14O8Mo, Mr = 406.19, Dc = 1.743g/cm3, m = 0.886mm-1, F(000) = 816, R = 0.0444 and wR = 0.1091 for 2336 observed reflections with I>2s(I). The average Mo=O bond length is 1.695(4) ? The two ketonic oxygen atoms of the pyranone moieties are trans to the oxo ligands and the hydroxy oxygen atoms are trans to each other. The average MoO bond lengths are 2.248(4) ?for the ketone oxygens and 2.005(3) ?for the hydroxy oxygens. The average ligand bite angle of OMoO is 75.2(2) and the bond angle between two Mo=O is 105.1(2). The dihedral angle is 79.16(2)?between two chelate ring planes.
