A nickel(Ⅱ) cluster,{[Ni(L)H2O]2(OAc)2Ni}.2EtOH,has been synthesized by the means of the complexation of nickel(Ⅱ) acetate tetrahydrate with a new Salen-type bisoxime ligand (H2L,4,4'-dimethoxy-2,2'-[ethylen...A nickel(Ⅱ) cluster,{[Ni(L)H2O]2(OAc)2Ni}.2EtOH,has been synthesized by the means of the complexation of nickel(Ⅱ) acetate tetrahydrate with a new Salen-type bisoxime ligand (H2L,4,4'-dimethoxy-2,2'-[ethylenedioxybis (nitrilo-methylidyne)]diphenol). The crystal structure shows that the hexacoodinated terminal nickel(Ⅱ) ions lie in the N2O2 coordination sphere of Salen-type bisoxime ligands,quadruple μ-phenoxo oxygen atoms from two [NiL] chelates coordinated to the central nickel(Ⅱ) ion,and the two acetate anions coordinated to three nickel(Ⅱ) ions through Ni-O-C-O-Ni bridges. Thus,all the three nickel atoms of the cluster have distorted octahedral geometries. CCDC:736762.展开更多
用非限制性密度泛函方法UBP86泛函结合def2-TZVP基组获得了Ni2～6团簇的几何结构并用ELF(ElectronLocalized Function)和LOL(Localized Orbital Locator)函数对小镍团簇的电子结构进行拓扑分析.研究结果表明,除Ni2团簇外,团簇中Ni—Ni...用非限制性密度泛函方法UBP86泛函结合def2-TZVP基组获得了Ni2～6团簇的几何结构并用ELF(ElectronLocalized Function)和LOL(Localized Orbital Locator)函数对小镍团簇的电子结构进行拓扑分析.研究结果表明,除Ni2团簇外,团簇中Ni—Ni键的成键临界点不在键轴上,为弯曲键.镍团簇中Ni—Ni间的金属键为部分共价键,其价层Basin的布局数均小于1e,并且团簇中存在多个多中心价层Basin.团簇中各个化学键均强烈离域化.团簇中的单电子主要位于内层轨道,并没有参与成键.展开更多
A Hydrothermal reaction of MoO 3, NiCl 2·6H 2O, WO 3 and H 2O with a molar ratio of 1∶0.6∶1∶83.3 gives a rhombic-shaped black crystal [NiMo 12O 40H 10{Ni(H 2O) 3} 4]. It crystallizes in a tetragonal system wit...A Hydrothermal reaction of MoO 3, NiCl 2·6H 2O, WO 3 and H 2O with a molar ratio of 1∶0.6∶1∶83.3 gives a rhombic-shaped black crystal [NiMo 12O 40H 10{Ni(H 2O) 3} 4]. It crystallizes in a tetragonal system with space group I4 1/amd and unit cell parameters a=b=1.518 4(2) nm, c=3.082 9(6) nm, Z=4, V=7.108(2) nm 3, R=0.067 1, wR=0.217 8. The compound possesses a four-capped Keggin structure. The structure of the Keggin- [NiMo 12O 40H 10] 8- consists of twelve MoO 6 octahedrons and a NiO 4 tetrahedron on the center. Four [Ni(H 2O) 3] 2+ at the cap positions are linked to Keggin-structure by three μ 3-O, respectively. The calculation of bond valence shows that the oxidation state of Mo in the compound is +5.展开更多
文摘A nickel(Ⅱ) cluster,{[Ni(L)H2O]2(OAc)2Ni}.2EtOH,has been synthesized by the means of the complexation of nickel(Ⅱ) acetate tetrahydrate with a new Salen-type bisoxime ligand (H2L,4,4'-dimethoxy-2,2'-[ethylenedioxybis (nitrilo-methylidyne)]diphenol). The crystal structure shows that the hexacoodinated terminal nickel(Ⅱ) ions lie in the N2O2 coordination sphere of Salen-type bisoxime ligands,quadruple μ-phenoxo oxygen atoms from two [NiL] chelates coordinated to the central nickel(Ⅱ) ion,and the two acetate anions coordinated to three nickel(Ⅱ) ions through Ni-O-C-O-Ni bridges. Thus,all the three nickel atoms of the cluster have distorted octahedral geometries. CCDC:736762.
文摘用非限制性密度泛函方法UBP86泛函结合def2-TZVP基组获得了Ni2～6团簇的几何结构并用ELF(ElectronLocalized Function)和LOL(Localized Orbital Locator)函数对小镍团簇的电子结构进行拓扑分析.研究结果表明,除Ni2团簇外,团簇中Ni—Ni键的成键临界点不在键轴上,为弯曲键.镍团簇中Ni—Ni间的金属键为部分共价键,其价层Basin的布局数均小于1e,并且团簇中存在多个多中心价层Basin.团簇中各个化学键均强烈离域化.团簇中的单电子主要位于内层轨道,并没有参与成键.
文摘A Hydrothermal reaction of MoO 3, NiCl 2·6H 2O, WO 3 and H 2O with a molar ratio of 1∶0.6∶1∶83.3 gives a rhombic-shaped black crystal [NiMo 12O 40H 10{Ni(H 2O) 3} 4]. It crystallizes in a tetragonal system with space group I4 1/amd and unit cell parameters a=b=1.518 4(2) nm, c=3.082 9(6) nm, Z=4, V=7.108(2) nm 3, R=0.067 1, wR=0.217 8. The compound possesses a four-capped Keggin structure. The structure of the Keggin- [NiMo 12O 40H 10] 8- consists of twelve MoO 6 octahedrons and a NiO 4 tetrahedron on the center. Four [Ni(H 2O) 3] 2+ at the cap positions are linked to Keggin-structure by three μ 3-O, respectively. The calculation of bond valence shows that the oxidation state of Mo in the compound is +5.
