Density functional theory（DFT） calculations unambiguously verify that there is little or no direct metalmetal bonding in the dinuclear copper（I） benzamidinate complex [Cu2（LRW）2]（2）{LRR=[PhC（NR）（NR＇）]-（R...Density functional theory（DFT） calculations unambiguously verify that there is little or no direct metalmetal bonding in the dinuclear copper（I） benzamidinate complex [Cu2（LRW）2]（2）{LRR=[PhC（NR）（NR＇）]-（R= 2,6-iPr2C6H3, R＇=SiMe3）} with a short Cu-Cu distance[0.24454（4） nm].展开更多
Due to the special structural feature and versatile reactivity towards various types of transformations,alkynes have inspired continuous research interest for their generation,incorporation and application in organic ...Due to the special structural feature and versatile reactivity towards various types of transformations,alkynes have inspired continuous research interest for their generation,incorporation and application in organic synthesis,chemical biology and material science[1].Notably,since its invention in 1975,the Sonogashira reaction,which efficiently couples aryl halides with aryl or vinyl terminal alkynes via Pd(0)/Cu(I)synergistic catalysis.展开更多
With respect to the first principle calculations, we predicted that two pairs of transition metals （e.g., Sc2 and Ti2） can be interbedded between two tetranitrogen rings to form two sandwich-like binuclear complexes...With respect to the first principle calculations, we predicted that two pairs of transition metals （e.g., Sc2 and Ti2） can be interbedded between two tetranitrogen rings to form two sandwich-like binuclear complexes respectively （e.g. N4Sc2N4 and NaTi2N4）. These two complexes can adsorb up to eight and ten hydrogen molecules, corresponding to a gravimetric storage capacity of 7.7 and 9.9 wt%, respectively. These sandwich-type complexes proposed in this work are favorable for reversible adsorption and desorption of hydrogen at ambient conditions. The results are helpful for the development of a new class of high-capacity hydrogen-storage media.展开更多
Two silver(I) complexes were obtained by the reaction of a N6 ligand with [Ag(PPh3)2(MeCN)](SbF6). In complex [AgL1(PPh3)](SbF6) 1, the silver center is bound to three N donors of the nitrogen ligand and P donor of ...Two silver(I) complexes were obtained by the reaction of a N6 ligand with [Ag(PPh3)2(MeCN)](SbF6). In complex [AgL1(PPh3)](SbF6) 1, the silver center is bound to three N donors of the nitrogen ligand and P donor of one triphenylphosphine group, forming an irregular AgN3P tetrahedron. In complex [Ag(PPh3)4](SbF6) 2, the Ag+ ion is coordinated to four triphenyl- phosphine groups, affording a tetrahedral geometry. Crystal data for complex 1: C30H37AgF6N6PSb, Mr = 856.25, orthorhombic, space group Pbca, a = 19.0702(9), b = 15.9047(7), c = 21.498(1) ?, V = 6520.5(6) ?3, Z = 8, Dc= 1.744 g/cm3, F(000) = 3408, μ = 1.544 mm-1, the final R = 0.0367 and wR = 0.1077 for 5325 observed reflections with I > 2σ(I); and those for 2: C72H60AgF6P4Sb, Mr = 1392.70, trigonal, space group R3, a = 14.4577(6), b = 14.4577(6), c = 51.544(2) ?, V = 9330.5(7) ?3, Z = 6, Dc= 1.487 g/cm3, F(000) = 4224, μ = 0.913 mm-1, the final R = 0.0352 and wR = 0.1089 for 3498 observed reflections with I > 2σ(I).展开更多
Three complexes, （PBT）W（CO）5 （1）, （3,5-Me2PBT）W（CO）5 （2） and （3,5- Pr2PBT）W（CO）5 （3） （PBT = 1H-（pyrazol-l-ylmethyl）-l,2,3-benzotriazole）, were synthesized, and two of them were structurally chara...Three complexes, （PBT）W（CO）5 （1）, （3,5-Me2PBT）W（CO）5 （2） and （3,5- Pr2PBT）W（CO）5 （3） （PBT = 1H-（pyrazol-l-ylmethyl）-l,2,3-benzotriazole）, were synthesized, and two of them were structurally characterized by X-ray crystallography. Complex 1 crystallizes in monoclinic with space group P21/c, α = 1.0828（2）, b = 2.1655（4）, c = 0.6982（1） nm, β = 93.39（3）°, V= 1.6343（6） nm3, Z = 4, Dc = 2.126 g/cms, F（000） = 992, β = 7.107 mm1, S = 0.990, the final R = 0.0301 and wR = 0.0685. Complex 2 crystallizes in triclinic with space group Pi, a = 0.95021（8）, b = 0.98391（6）, c - 1.1433（1） nm, α = 68.792（7）, β = 77.860（8）, γ= 75.533（6）°, V= 0.9563（1） nm3, Z = 2, Dc = 1.914 g/cm3, F（000） = 528, β = 6.078 mm-1, S = 1.042, the final R = 0.0253 and wR = 0.0549. 1H-（Pyrazol-l-ylmethyl）-l,2,3-benzotriazoles acted as monodentate ligands through the 3-position nitrogen of the triazolyl group, and the pyrazolyl nitrogen did not participate in coordinating to the metal centers in these complexes. Their UV and fluorescence properties have been studied.展开更多
基金Supported by the National Natural Science Foundation of China（No.21201006）, the Special Research Fund for the Doctoral Program of Higher Education of China（No.26920123415120002） and the Fund of the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of China（No.2012-27）.Acknowledgements We thank Prof ZHANG Hongjie（Changchun Institute of Applied Chemistry, Chinese Academy of Sciences） for his helpful suggestions.
文摘Density functional theory（DFT） calculations unambiguously verify that there is little or no direct metalmetal bonding in the dinuclear copper（I） benzamidinate complex [Cu2（LRW）2]（2）{LRR=[PhC（NR）（NR＇）]-（R= 2,6-iPr2C6H3, R＇=SiMe3）} with a short Cu-Cu distance[0.24454（4） nm].
文摘Due to the special structural feature and versatile reactivity towards various types of transformations,alkynes have inspired continuous research interest for their generation,incorporation and application in organic synthesis,chemical biology and material science[1].Notably,since its invention in 1975,the Sonogashira reaction,which efficiently couples aryl halides with aryl or vinyl terminal alkynes via Pd(0)/Cu(I)synergistic catalysis.
基金Supported by the Special Fund of Shaanxi Province Education Bureau (No. 2010JK548)Shaanxi Natural Science Foundation Research Programs (No. 2011JM6005)
文摘With respect to the first principle calculations, we predicted that two pairs of transition metals （e.g., Sc2 and Ti2） can be interbedded between two tetranitrogen rings to form two sandwich-like binuclear complexes respectively （e.g. N4Sc2N4 and NaTi2N4）. These two complexes can adsorb up to eight and ten hydrogen molecules, corresponding to a gravimetric storage capacity of 7.7 and 9.9 wt%, respectively. These sandwich-type complexes proposed in this work are favorable for reversible adsorption and desorption of hydrogen at ambient conditions. The results are helpful for the development of a new class of high-capacity hydrogen-storage media.
基金This work was supported by the NSF of Fujian Province (E0310029)and the Innovation Fund of Fujian Province (2003J044)
文摘Two silver(I) complexes were obtained by the reaction of a N6 ligand with [Ag(PPh3)2(MeCN)](SbF6). In complex [AgL1(PPh3)](SbF6) 1, the silver center is bound to three N donors of the nitrogen ligand and P donor of one triphenylphosphine group, forming an irregular AgN3P tetrahedron. In complex [Ag(PPh3)4](SbF6) 2, the Ag+ ion is coordinated to four triphenyl- phosphine groups, affording a tetrahedral geometry. Crystal data for complex 1: C30H37AgF6N6PSb, Mr = 856.25, orthorhombic, space group Pbca, a = 19.0702(9), b = 15.9047(7), c = 21.498(1) ?, V = 6520.5(6) ?3, Z = 8, Dc= 1.744 g/cm3, F(000) = 3408, μ = 1.544 mm-1, the final R = 0.0367 and wR = 0.1077 for 5325 observed reflections with I > 2σ(I); and those for 2: C72H60AgF6P4Sb, Mr = 1392.70, trigonal, space group R3, a = 14.4577(6), b = 14.4577(6), c = 51.544(2) ?, V = 9330.5(7) ?3, Z = 6, Dc= 1.487 g/cm3, F(000) = 4224, μ = 0.913 mm-1, the final R = 0.0352 and wR = 0.1089 for 3498 observed reflections with I > 2σ(I).
基金supported by the National Natural Science Foundation of China(No.21372124)NFFTBS(No.J1103306)
文摘Three complexes, （PBT）W（CO）5 （1）, （3,5-Me2PBT）W（CO）5 （2） and （3,5- Pr2PBT）W（CO）5 （3） （PBT = 1H-（pyrazol-l-ylmethyl）-l,2,3-benzotriazole）, were synthesized, and two of them were structurally characterized by X-ray crystallography. Complex 1 crystallizes in monoclinic with space group P21/c, α = 1.0828（2）, b = 2.1655（4）, c = 0.6982（1） nm, β = 93.39（3）°, V= 1.6343（6） nm3, Z = 4, Dc = 2.126 g/cms, F（000） = 992, β = 7.107 mm1, S = 0.990, the final R = 0.0301 and wR = 0.0685. Complex 2 crystallizes in triclinic with space group Pi, a = 0.95021（8）, b = 0.98391（6）, c - 1.1433（1） nm, α = 68.792（7）, β = 77.860（8）, γ= 75.533（6）°, V= 0.9563（1） nm3, Z = 2, Dc = 1.914 g/cm3, F（000） = 528, β = 6.078 mm-1, S = 1.042, the final R = 0.0253 and wR = 0.0549. 1H-（Pyrazol-l-ylmethyl）-l,2,3-benzotriazoles acted as monodentate ligands through the 3-position nitrogen of the triazolyl group, and the pyrazolyl nitrogen did not participate in coordinating to the metal centers in these complexes. Their UV and fluorescence properties have been studied.
