Two Mo/S complexes:K6[Mo2O2S2（C2O4）2（ClPO3）2]·H2O（1）andK6[Mo2O3S（C2O4）2（ClPO3）2]·3H2O（2）containing oxalate ligand were prepared by the reaction of（NH4）2MoS4 and potassiu oxalate with adding a s...Two Mo/S complexes:K6[Mo2O2S2（C2O4）2（ClPO3）2]·H2O（1）andK6[Mo2O3S（C2O4）2（ClPO3）2]·3H2O（2）containing oxalate ligand were prepared by the reaction of（NH4）2MoS4 and potassiu oxalate with adding a small amount of H3PO4 to adjust the value of pH in system of methanol and water under an atmosphere of pure nitrogen at ambient temperature and charcterized by the means of elemental analysis,IR,UV-vis.The analysis results reveal that crystal of the complex 1 is Orthorhombic,space group pbcn,a=4.6370（2）nm,b=0.7549（2）nm,c=1.3888（4）nm,V=4.861（2）nm3,Z=8,Mr=945.49,Dc=2.58g/cm3,μ=2.625cm-1,R=0.063,wR=0.075.In addition,The their spectral properties were also discussed.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
A novel compound [(CH 3CH 2) 4N] 4[(La 12 (OH) 12 MoO 29 )] was synthesized by hydrothermal reaction. The single crystal X ray diffraction shows that the compound crystallized in the monoclinic space group C2/c ; a =2...A novel compound [(CH 3CH 2) 4N] 4[(La 12 (OH) 12 MoO 29 )] was synthesized by hydrothermal reaction. The single crystal X ray diffraction shows that the compound crystallized in the monoclinic space group C2/c ; a =2 5729(4) nm, b =1 4318(1) nm, c =2 1217(4) nm, β =111 56(1)°, V =6 8235(7) nm 3, Z =4, R =0 0751. The basic building blocks of the crystal structure included one MoO 5 hexahedron and twelve LaO 6 octahedra which shared a common edge to form a [(La 12 (OH) 12 MoO 29 )] 4- unit. These units were held together by the [(CH 3CH 2) 4N] + ions.展开更多
Molybdenum (VI) complex, namely molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] used as epoxidation catalyst species, was synthesized and characterized by elemental analysis and infrared spectrum. Polystyrene-supp...Molybdenum (VI) complex, namely molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] used as epoxidation catalyst species, was synthesized and characterized by elemental analysis and infrared spectrum. Polystyrene-supported molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] for synthesis of epoxycyclohexane was prepared by phase transfer catalysis method. Effects of various factors in synthesis of epoxycyclohexane by reaction of cyclohexene and t-BuOOH in the atmosphere of nitrogen catalyzed by polystyrene-supported MoO2(acac)2 were also investigated. Under the following conditions, n(cyclohexene):n(t-BuOOH)=3.5:l (based on 0.1 mol of t-BuOOH), volume of solvent -10ml, reaction temperature -80℃, reaction time -60min, and mass of molybdenum in the catalyst -2.30×0^(-3)g, the yield of epoxycyclohexane on the basis of t-BuOOH is over 99.5%, and the purity of epoxycyclohexane is about 99.9% by gas chromatogram(GC) analysis.展开更多
The cubane-type mixed Mo W cluster[Mo2W2S4 (OAc)2(dtp)3 (dtpH)]·CH2Cl2 (dtp= (EtO)2PS2, dtpH = (EtO)2PS (SH) has been prepared by reduction and addition reaction between dinuclear W2S4 (dtp)2 and Mo(CO)6 in HOAc...The cubane-type mixed Mo W cluster[Mo2W2S4 (OAc)2(dtp)3 (dtpH)]·CH2Cl2 (dtp= (EtO)2PS2, dtpH = (EtO)2PS (SH) has been prepared by reduction and addition reaction between dinuclear W2S4 (dtp)2 and Mo(CO)6 in HOAc and Ac2O solution in the presence of dtp-ligand. Crystallographic data: Mr=1632. 71,monoclinic, space group P2/n, a=13. 146 (8), b=11. 961 (5),c=17. 157 (9) β =105. 99(8)°, V=2593(8), Z=2, Dc=2. 09 /cm￣3 ,λ(MoKa) =0.71073 ,F (000)=1578, final R=0. 029, Rw = 0. 041 for 3765 unique intensity data [I≥4σ (I)]. The result of X-ray study and elemental analysis indicated that, in the crystal lattice, molybdenum and tungsten are statistically distributed in the metal positions each with 0. 5 fractional occupation.展开更多
文摘Two Mo/S complexes:K6[Mo2O2S2（C2O4）2（ClPO3）2]·H2O（1）andK6[Mo2O3S（C2O4）2（ClPO3）2]·3H2O（2）containing oxalate ligand were prepared by the reaction of（NH4）2MoS4 and potassiu oxalate with adding a small amount of H3PO4 to adjust the value of pH in system of methanol and water under an atmosphere of pure nitrogen at ambient temperature and charcterized by the means of elemental analysis,IR,UV-vis.The analysis results reveal that crystal of the complex 1 is Orthorhombic,space group pbcn,a=4.6370（2）nm,b=0.7549（2）nm,c=1.3888（4）nm,V=4.861（2）nm3,Z=8,Mr=945.49,Dc=2.58g/cm3,μ=2.625cm-1,R=0.063,wR=0.075.In addition,The their spectral properties were also discussed.
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.
基金Supported by the National Natural Science Foundation of China(No.2 0 1710 10 )
文摘A novel compound [(CH 3CH 2) 4N] 4[(La 12 (OH) 12 MoO 29 )] was synthesized by hydrothermal reaction. The single crystal X ray diffraction shows that the compound crystallized in the monoclinic space group C2/c ; a =2 5729(4) nm, b =1 4318(1) nm, c =2 1217(4) nm, β =111 56(1)°, V =6 8235(7) nm 3, Z =4, R =0 0751. The basic building blocks of the crystal structure included one MoO 5 hexahedron and twelve LaO 6 octahedra which shared a common edge to form a [(La 12 (OH) 12 MoO 29 )] 4- unit. These units were held together by the [(CH 3CH 2) 4N] + ions.
基金Supported by the Outstanding Personality Innovation Funds of Henan Province(No.0121001900).
文摘Molybdenum (VI) complex, namely molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] used as epoxidation catalyst species, was synthesized and characterized by elemental analysis and infrared spectrum. Polystyrene-supported molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] for synthesis of epoxycyclohexane was prepared by phase transfer catalysis method. Effects of various factors in synthesis of epoxycyclohexane by reaction of cyclohexene and t-BuOOH in the atmosphere of nitrogen catalyzed by polystyrene-supported MoO2(acac)2 were also investigated. Under the following conditions, n(cyclohexene):n(t-BuOOH)=3.5:l (based on 0.1 mol of t-BuOOH), volume of solvent -10ml, reaction temperature -80℃, reaction time -60min, and mass of molybdenum in the catalyst -2.30×0^(-3)g, the yield of epoxycyclohexane on the basis of t-BuOOH is over 99.5%, and the purity of epoxycyclohexane is about 99.9% by gas chromatogram(GC) analysis.
文摘The cubane-type mixed Mo W cluster[Mo2W2S4 (OAc)2(dtp)3 (dtpH)]·CH2Cl2 (dtp= (EtO)2PS2, dtpH = (EtO)2PS (SH) has been prepared by reduction and addition reaction between dinuclear W2S4 (dtp)2 and Mo(CO)6 in HOAc and Ac2O solution in the presence of dtp-ligand. Crystallographic data: Mr=1632. 71,monoclinic, space group P2/n, a=13. 146 (8), b=11. 961 (5),c=17. 157 (9) β =105. 99(8)°, V=2593(8), Z=2, Dc=2. 09 /cm￣3 ,λ(MoKa) =0.71073 ,F (000)=1578, final R=0. 029, Rw = 0. 041 for 3765 unique intensity data [I≥4σ (I)]. The result of X-ray study and elemental analysis indicated that, in the crystal lattice, molybdenum and tungsten are statistically distributed in the metal positions each with 0. 5 fractional occupation.
