A new mixed-valence oxo-centered trinuclear manganese complex Mn3O(O2CPh)6 (Py)3 was prepared in pyridine solvent and its crystal structure has been determined. C57H45O13N3Mn3, Mr =1144. 81, trigonal, space group R3,...A new mixed-valence oxo-centered trinuclear manganese complex Mn3O(O2CPh)6 (Py)3 was prepared in pyridine solvent and its crystal structure has been determined. C57H45O13N3Mn3, Mr =1144. 81, trigonal, space group R3,(No.148), unit cell parameters(H cell): a=b=43. 605 (7), c=15. 756(4), V =25946(10),Z=18, Dc=1.32 g/cm￣3 , F(000) = 10566.The final values of R and Rw are 0. 098 and 0. 087 respectively for 3087 observed reflections with Ⅰ>4σ(Ⅰ). The distances of Mn(1)-O(1), Mn(2)-O(1) and Mn(3)-O(1) are 1.855(10),1. 817(8) and 2. 089 (8), respectively, indicating the title compound is a valence-trapped situation.展开更多
A new mixed-valence cyanide-bridged complex, Br3Fe（p-NC）RuBr（dppm）2 （dppm = bis（diphenylphosphino）methane）, was obtained through the reaction between trans-（dppm）2C1- RuCN and FeBr3. Its crystal structure wa...A new mixed-valence cyanide-bridged complex, Br3Fe（p-NC）RuBr（dppm）2 （dppm = bis（diphenylphosphino）methane）, was obtained through the reaction between trans-（dppm）2C1- RuCN and FeBr3. Its crystal structure was characterized. Electronic absorption spectra indicate the existence of metal-to-metal charge transfer （MMCT） and this complex is Class II mixed valence complexes according to the classification of Robin and Day. Magnetic analysis shows it is paramagnetic.展开更多
The title compound was prepared by solid state reaction of LaCl_3/V inan evacuated silica tube where the silicon came from the reaction tube. The compoundcrystallizes in monoclinic space group C2/m with cell dimension...The title compound was prepared by solid state reaction of LaCl_3/V inan evacuated silica tube where the silicon came from the reaction tube. The compoundcrystallizes in monoclinic space group C2/m with cell dimensions of a=13. 482 (7), b=5. 604(3), c=11. 091(3) A, β=100. 44(3)°, V=824(1) A3, Mr= 1274. 66 , Dc=5. 14 g/cm3, F(000) = 1150, μ- 13. 20 mm-1 and Z=2; final R=0. 061, Rw=0. 054for 1037 observed reflections (Ⅰ>3σ(Ⅰ) ) . It is isostructural with quasi-ZD Pr_4V_5Si_4O_(22)compound with the Ⅴ-Ⅴ distances across the shared VO6 octahedral edges of 2. 802 Aand vanadium ions show mixed-valence(Ⅲ/Ⅳ) with an average value of+ 3. 2.展开更多
Copper (Ⅱ) α-methacrylate reacts with triphenylphosphine to form whxed-valence copper (Ⅰ,Ⅱ) complex Cu4(CH2=C(CH3)COO)6(PPh3)4(CH3OH）2 in methanol solution. The crystal and molecular structure of the complex has ...Copper (Ⅱ) α-methacrylate reacts with triphenylphosphine to form whxed-valence copper (Ⅰ,Ⅱ) complex Cu4(CH2=C(CH3)COO)6(PPh3)4(CH3OH）2 in methanol solution. The crystal and molecular structure of the complex has been detendned by single crystal X-ray structural analysis. This material forms pale green crystals with triclinic symmetry, space group Pi, a=1 .3567(2) nm, b=1.3946 (3) nm, c=1.4569 (3) nm, α=66.069 (14)0, β=84.234 (14)0 γ=69.975 (13)0,R=0.0536.展开更多
Reaction of a tripodal ligand, N,N＇,N＇＇-tris（3-pyridinyl） phosphoric trimide（TPPA） and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-...Reaction of a tripodal ligand, N,N＇,N＇＇-tris（3-pyridinyl） phosphoric trimide（TPPA） and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964（5）, b = 10.2592, c = 10.5822（8） A, V = 933.01（9） A3, Z = 2, C_（30）H_（24）Br_4Cu_3N_（12）O_2P_2, M_r = 985.02, D_c = 1.753 g/cm3, F（000） = 4072 and μ（MoKα） = 0.746 mm^（-1）. The final R and w R are 0.0588 and 0.1329 for 4260 observed reflections with I 〉 2σ（I）. Cu（Ⅰ） is tetrahedrally coordinated and Cu（Ⅱ） center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N-H···O and N-H···Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.展开更多
A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoc...A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I＞2σ (Ⅰ)].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
The half Dawson structure complex has been prepared by reaction of Na2WO4·2H2O, Na2MoO4·2H2O and NaH2PO4 in water. 4H3[PW6Mo4Cu2O38(H2O)2] have been synthesized by reaction of 9- and Cu2+ in water and recrys...The half Dawson structure complex has been prepared by reaction of Na2WO4·2H2O, Na2MoO4·2H2O and NaH2PO4 in water. 4H3[PW6Mo4Cu2O38(H2O)2] have been synthesized by reaction of 9- and Cu2+ in water and recrystallized in a mixed acetone/water solvent. They were characterized by elemental analyses, IR spectra and electronic spectra. The crystal structure of 4H3[PW6Mo4Cu2O38(H2O)2] has been determined by X ray structure analysis for the first time, which belongs to trigonal with space group R 3, a=b=c=1.53081 (18) nm, α=β=γ=109.458(17)°, Z=1, Dc=3.141Mg·m-3, R=0.0780, Rw=0.1480. The sites of the molybdenum, tungsten and copper atoms are disordered over 12 possible locations in the crystal, and the anion has a high symmetry due to the disorder of the molybdenum, tungsten and copper atoms. CCDC: 176656.展开更多
文摘A new mixed-valence oxo-centered trinuclear manganese complex Mn3O(O2CPh)6 (Py)3 was prepared in pyridine solvent and its crystal structure has been determined. C57H45O13N3Mn3, Mr =1144. 81, trigonal, space group R3,(No.148), unit cell parameters(H cell): a=b=43. 605 (7), c=15. 756(4), V =25946(10),Z=18, Dc=1.32 g/cm￣3 , F(000) = 10566.The final values of R and Rw are 0. 098 and 0. 087 respectively for 3087 observed reflections with Ⅰ>4σ(Ⅰ). The distances of Mn(1)-O(1), Mn(2)-O(1) and Mn(3)-O(1) are 1.855(10),1. 817(8) and 2. 089 (8), respectively, indicating the title compound is a valence-trapped situation.
基金supported by the 973 Program(2012CB821702,2014CB845603)the National Natural Science Foundation of China(21233009,21203194 and 21173223)
文摘A new mixed-valence cyanide-bridged complex, Br3Fe（p-NC）RuBr（dppm）2 （dppm = bis（diphenylphosphino）methane）, was obtained through the reaction between trans-（dppm）2C1- RuCN and FeBr3. Its crystal structure was characterized. Electronic absorption spectra indicate the existence of metal-to-metal charge transfer （MMCT） and this complex is Class II mixed valence complexes according to the classification of Robin and Day. Magnetic analysis shows it is paramagnetic.
文摘The title compound was prepared by solid state reaction of LaCl_3/V inan evacuated silica tube where the silicon came from the reaction tube. The compoundcrystallizes in monoclinic space group C2/m with cell dimensions of a=13. 482 (7), b=5. 604(3), c=11. 091(3) A, β=100. 44(3)°, V=824(1) A3, Mr= 1274. 66 , Dc=5. 14 g/cm3, F(000) = 1150, μ- 13. 20 mm-1 and Z=2; final R=0. 061, Rw=0. 054for 1037 observed reflections (Ⅰ>3σ(Ⅰ) ) . It is isostructural with quasi-ZD Pr_4V_5Si_4O_(22)compound with the Ⅴ-Ⅴ distances across the shared VO6 octahedral edges of 2. 802 Aand vanadium ions show mixed-valence(Ⅲ/Ⅳ) with an average value of+ 3. 2.
文摘Copper (Ⅱ) α-methacrylate reacts with triphenylphosphine to form whxed-valence copper (Ⅰ,Ⅱ) complex Cu4(CH2=C(CH3)COO)6(PPh3)4(CH3OH）2 in methanol solution. The crystal and molecular structure of the complex has been detendned by single crystal X-ray structural analysis. This material forms pale green crystals with triclinic symmetry, space group Pi, a=1 .3567(2) nm, b=1.3946 (3) nm, c=1.4569 (3) nm, α=66.069 (14)0, β=84.234 (14)0 γ=69.975 (13)0,R=0.0536.
基金supported by the Natural Science Foundation of Shanxi province(2012021005-2)Technology Foundation for Selected Overseas of Shanxi
文摘Reaction of a tripodal ligand, N,N＇,N＇＇-tris（3-pyridinyl） phosphoric trimide（TPPA） and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964（5）, b = 10.2592, c = 10.5822（8） A, V = 933.01（9） A3, Z = 2, C_（30）H_（24）Br_4Cu_3N_（12）O_2P_2, M_r = 985.02, D_c = 1.753 g/cm3, F（000） = 4072 and μ（MoKα） = 0.746 mm^（-1）. The final R and w R are 0.0588 and 0.1329 for 4260 observed reflections with I 〉 2σ（I）. Cu（Ⅰ） is tetrahedrally coordinated and Cu（Ⅱ） center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N-H···O and N-H···Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.
文摘A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I＞2σ (Ⅰ)].
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.
文摘The half Dawson structure complex has been prepared by reaction of Na2WO4·2H2O, Na2MoO4·2H2O and NaH2PO4 in water. 4H3[PW6Mo4Cu2O38(H2O)2] have been synthesized by reaction of 9- and Cu2+ in water and recrystallized in a mixed acetone/water solvent. They were characterized by elemental analyses, IR spectra and electronic spectra. The crystal structure of 4H3[PW6Mo4Cu2O38(H2O)2] has been determined by X ray structure analysis for the first time, which belongs to trigonal with space group R 3, a=b=c=1.53081 (18) nm, α=β=γ=109.458(17)°, Z=1, Dc=3.141Mg·m-3, R=0.0780, Rw=0.1480. The sites of the molybdenum, tungsten and copper atoms are disordered over 12 possible locations in the crystal, and the anion has a high symmetry due to the disorder of the molybdenum, tungsten and copper atoms. CCDC: 176656.
