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
Compound[(n-C4H9)4N]3 [Mo6O18(N2C6H4-pNO2)] crystallizes in the orthorhombic space grou Pnma with a= 23. 964(9).b=16.948(4),c=17.968(7) A,V=7298(7) A3,Z=4,and Dc=1.58 g/cm-3. Structure solution and refinement based on...Compound[(n-C4H9)4N]3 [Mo6O18(N2C6H4-pNO2)] crystallizes in the orthorhombic space grou Pnma with a= 23. 964(9).b=16.948(4),c=17.968(7) A,V=7298(7) A3,Z=4,and Dc=1.58 g/cm-3. Structure solution and refinement based on 3113 reflections with I>3.0σ(I) gave final residuals of R= 0.072 and Rω=0.099.The anion is a substitution isopolymolybdate.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 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
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 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
Both of the title complexes were produced by oxidative decarbony-lation of NH4 CMO (CO)5I]. The complexes CMo(S2CNC4H8)4]I3 ?C7H8(1) and Mo2S2O2 (S2CNC4H8)2(2) both crystallize in triclinic, space group P1 with cell d...Both of the title complexes were produced by oxidative decarbony-lation of NH4 CMO (CO)5I]. The complexes CMo(S2CNC4H8)4]I3 ?C7H8(1) and Mo2S2O2 (S2CNC4H8)2(2) both crystallize in triclinic, space group P1 with cell dimensions for (1) : a=13. 554(4), b=13. 620(4), c= 13. 058 (4) A , α=95. 58 (3), β=105. 38(2), γ=115. 49(2)°,V = 2035(1) A3, Z=2, Dc=1. 89 g. cm-3, final R=0. 054 and Rw = 0. 062 for 2926 observed reflections; and for (2): a = 8.730(2), b=16.592(6), c = 6. 688(2)A, α=97. 67(3), β=98. 10(2), γ=80. 26(2)% V = 939. 2(5) A3, Z = 2, Dc = 2. 05 g. cm-3, final R = 0. 038 and Rw = 0. 046 for 2248 observed reflections. The Mo(V) atom is bonded to eight S atoms in distorted dodecahedron for (1). The Mo atoms in compound (2) are bridged by two S atoms and each Mo atom is coordinated by two S atoms from S2CNC4H8 and one O atom to form distorted tetragonal pyramid.展开更多
The reaction of Mo(0) complex [Mo(CO)_4(S_2CNEt_2)]^- with phenthiolate [Et_4N]SΦ in acetonitrilo in the presence of small amount of air affords a new oxo-molybdenum com- plex [MoO(SΦ)_2(S_2CNEt_2)]^-,which crystall...The reaction of Mo(0) complex [Mo(CO)_4(S_2CNEt_2)]^- with phenthiolate [Et_4N]SΦ in acetonitrilo in the presence of small amount of air affords a new oxo-molybdenum com- plex [MoO(SΦ)_2(S_2CNEt_2)]^-,which crystallizes in two forms of crystals,[Et_4N][MoO(SΦ)_2 (S_2CNEt_2)](1a) and [Et_4N][MoO(SΦ)_2(S_2CNEt_2)]·(CH_3)_2CHOH (1b).The structures of 1a and 1b were determined from three-dimensional X-ray data.1a crystallizes in the mo- noclinie,space group C_c with a=12.321(4),b=15.245(4),c=16.087(9);β=98.44(4)°.V= 2989~3,Z=4,D_c=1.35 g/cm^3 and R=0.031 for 2434 reflections [I>3(I)].1b crystallizes in the monoclinic,space group P2_1/n with a=9.861(1),b=20.357(3),c=17.122(5)A;β=92.27 (2)°,V=3434.3~3,Z=4;D_c=1.29 g/cm^3 and R=0.051 for 2852 independeut reflections [I> 3σ(I)],The structures of 1a and 1b reveal that the anion [MoO(SΦ)_2(S_2CNEt_2)]^- contains a single oxo ligand coordinating to a molybdenum(Ⅳ) and the geometry around Me(Ⅳ) atom is a distorted square pyramid.Interestingly,the solvate molecule isopropanol of 1b is linked to oxo group by a hydrogen-bond of 1.928A,leading to the increase of Mo=O bond distance (1.718).Mo—S distances are 2.44 and 2,39.The electrochemical behavior of 1 was discussed also.展开更多
Mixed-valence dinuclear molybdenum complex [Et4N][Mo2(PyS)3(CO)5] (1) (PyS=C5H4NS) has been synthe-sized and characterized by crystallography. 1 crystallizes in monoclinic system with space group P21/c with a=1.5769(1...Mixed-valence dinuclear molybdenum complex [Et4N][Mo2(PyS)3(CO)5] (1) (PyS=C5H4NS) has been synthe-sized and characterized by crystallography. 1 crystallizes in monoclinic system with space group P21/c with a=1.5769(11) nm, b=1.3144(5) nm, c=1.6935(10) nm; b=111.20(4); V=3.2724 nm3; Z=4, Dc=1.61 g/cm3, =9.7 cm-1 and F(000)=1600. The final R=0.054 and wR=0.073, for 1811 observed reflection with I>3s(I). In compound 1, one chelating PyS ligand and two bridging PyS ligands are 3-electron and 5-electron donors, respec-tively, and two molybdenum atoms are located in different coordination environments resulting in mixed-valence state. The reaction mechanism of Mo(CO)6 with PySH and PySO (C5H5SNO) was investigated and two reac-tion pathways were proposed.展开更多
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Compound[(n-C4H9)4N]3 [Mo6O18(N2C6H4-pNO2)] crystallizes in the orthorhombic space grou Pnma with a= 23. 964(9).b=16.948(4),c=17.968(7) A,V=7298(7) A3,Z=4,and Dc=1.58 g/cm-3. Structure solution and refinement based on 3113 reflections with I>3.0σ(I) gave final residuals of R= 0.072 and Rω=0.099.The anion is a substitution isopolymolybdate.
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 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.
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Both of the title complexes were produced by oxidative decarbony-lation of NH4 CMO (CO)5I]. The complexes CMo(S2CNC4H8)4]I3 ?C7H8(1) and Mo2S2O2 (S2CNC4H8)2(2) both crystallize in triclinic, space group P1 with cell dimensions for (1) : a=13. 554(4), b=13. 620(4), c= 13. 058 (4) A , α=95. 58 (3), β=105. 38(2), γ=115. 49(2)°,V = 2035(1) A3, Z=2, Dc=1. 89 g. cm-3, final R=0. 054 and Rw = 0. 062 for 2926 observed reflections; and for (2): a = 8.730(2), b=16.592(6), c = 6. 688(2)A, α=97. 67(3), β=98. 10(2), γ=80. 26(2)% V = 939. 2(5) A3, Z = 2, Dc = 2. 05 g. cm-3, final R = 0. 038 and Rw = 0. 046 for 2248 observed reflections. The Mo(V) atom is bonded to eight S atoms in distorted dodecahedron for (1). The Mo atoms in compound (2) are bridged by two S atoms and each Mo atom is coordinated by two S atoms from S2CNC4H8 and one O atom to form distorted tetragonal pyramid.
基金Project supported by the National Natural Science Foundation of China and the Natural Science Foundation of Chinese Academy of Sciences.
文摘The reaction of Mo(0) complex [Mo(CO)_4(S_2CNEt_2)]^- with phenthiolate [Et_4N]SΦ in acetonitrilo in the presence of small amount of air affords a new oxo-molybdenum com- plex [MoO(SΦ)_2(S_2CNEt_2)]^-,which crystallizes in two forms of crystals,[Et_4N][MoO(SΦ)_2 (S_2CNEt_2)](1a) and [Et_4N][MoO(SΦ)_2(S_2CNEt_2)]·(CH_3)_2CHOH (1b).The structures of 1a and 1b were determined from three-dimensional X-ray data.1a crystallizes in the mo- noclinie,space group C_c with a=12.321(4),b=15.245(4),c=16.087(9);β=98.44(4)°.V= 2989~3,Z=4,D_c=1.35 g/cm^3 and R=0.031 for 2434 reflections [I>3(I)].1b crystallizes in the monoclinic,space group P2_1/n with a=9.861(1),b=20.357(3),c=17.122(5)A;β=92.27 (2)°,V=3434.3~3,Z=4;D_c=1.29 g/cm^3 and R=0.051 for 2852 independeut reflections [I> 3σ(I)],The structures of 1a and 1b reveal that the anion [MoO(SΦ)_2(S_2CNEt_2)]^- contains a single oxo ligand coordinating to a molybdenum(Ⅳ) and the geometry around Me(Ⅳ) atom is a distorted square pyramid.Interestingly,the solvate molecule isopropanol of 1b is linked to oxo group by a hydrogen-bond of 1.928A,leading to the increase of Mo=O bond distance (1.718).Mo—S distances are 2.44 and 2,39.The electrochemical behavior of 1 was discussed also.
基金Project supported by the National Natural Science Foundation of China (No. 29733090-3) and State Key Laboratory of Structural Chemistry.
文摘Mixed-valence dinuclear molybdenum complex [Et4N][Mo2(PyS)3(CO)5] (1) (PyS=C5H4NS) has been synthe-sized and characterized by crystallography. 1 crystallizes in monoclinic system with space group P21/c with a=1.5769(11) nm, b=1.3144(5) nm, c=1.6935(10) nm; b=111.20(4); V=3.2724 nm3; Z=4, Dc=1.61 g/cm3, =9.7 cm-1 and F(000)=1600. The final R=0.054 and wR=0.073, for 1811 observed reflection with I>3s(I). In compound 1, one chelating PyS ligand and two bridging PyS ligands are 3-electron and 5-electron donors, respec-tively, and two molybdenum atoms are located in different coordination environments resulting in mixed-valence state. The reaction mechanism of Mo(CO)6 with PySH and PySO (C5H5SNO) was investigated and two reac-tion pathways were proposed.
