Synthesis and catalysis of di- and tetranuclear metal sandwich-type silicotungstates [(γ-SiW10O36)2M 2(μ-OH)2]10- and [(γ-SiW 10O36)2M4(μ4-O) (μ-OH)6]8- (M = Zr or Hf)

被引：0
|
作者：
Kikukawa, Yuji [1 ]
Yamaguchi, Syuhei [2 ]
Tsuchida, Kazutaka [1 ]
Nakagawa, Yoshinao [1 ]
Uehara, Kazuhiro [1 ,2 ]
Yamaguchi, Kazuya [1 ,2 ]
Mizuno, Noritaka [1 ,2 ]
机构：
[1] Department of Applied Chemistry, School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
[2] Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan
来源：
Journal of the American Chemical Society | 2008年 / 130卷 / 16期
关键词：
The di- and tetranuclear metal sandwich-type silicotungstates of Cs 10[(γ-SiW10O36)2{Zr(H 2O)}2(μ-OH)2]&middot18H2O (Zr2; monoclinic; C2/c; (No; 15); a; 25.3315(8); Å; b; 22.6699(7); c; 18.5533(6); β; 123.9000(12)°; V; 8843.3(5); Å3; Z; 4); Cs10[(γ-SiW10O; 36)2{Hf(H2O)}2(μ-OH); 2]&middot17H2O; (Hf2; space group C2/c (No. 15); 25.3847(16); 22.6121(14); 18.8703(11); 124.046(3)°; 8974.9(9); Cs 8[(γ-SiW10O36)2{Zr(H 2O)}4(μ4-O)(μ-OH)6] &middot26H2O (Zr4; tetragonal; P41212; 92); 12.67370(10); 61.6213(8); 9897.78(17); and Cs8[(γ-SiW10O 36)2{Hf(H2O)}4(μ4-O) (μ-OH)6]&middot23H2O (Hf4; P4; 1212; 12.68130(10); 61.5483(9); 9897.91(18); Z = 4) were obtained as single crystals suitable for X-ray crystallographic analyses by the reaction of a dilacunary γ-Keggin silicotungstate K8[γ-SiW 10O36] with ZrOCl2&middot8H2O or HfOCl2&middot8H2O. These dimeric polyoxometalates consisted of two [γ-SiW10O36]8- units sandwiching metal-oxygen clusters such as [M2(μ-OH) 2]6+ and [M4(μ4-O)(μ-OH) 6]8+ (M = Zr or Hf). The dinuclear zirconium and hafnium complexes Zr2 and Hf2 were isostructural. The equatorially placed two metal atoms in Zr2 and Hf2 were linked by two μ-OH ligands and each metal was bound to four oxygen atoms of two [γ-SiW10O36] 8- units. The tertanuclear zirconium and hafnium complexes Zr4 and Hf4 were isostructural and consisted of the adamantanoid cages with a tetracoordinated oxygen atom in the middle; M4(μ4-O) (μ-OH)6]8+ (M = Zr or Hf). Each metal atom in Zr4 and Hf4 was linked by three μ-OH ligands and bound to two oxygen atoms of the [γ-SiW10O36]8- unit. The tetra-nuclear zirconium and hafnium complexes showed catalytic activity for the intramolecular cyclization of (+)-citronellal to isopulegols without formation of byproducts resulting from etherification and dehydration. A lacunary silicotungstate [γ-SiW10O34(H2O)2] 4- was inactive; and the isomer ratio of isopulegols in the presence of MOCl2&middot8H2O (M = Zr or Hf) were much different from that in the presence of tetranuclear complexes; suggesting that the [M 4(μ4-O)(μ-OH)6]8+ core incorporated into the POM frameworks acts as an active site for the present cyclization. On the other hand; the reaction hardly proceeded in the presence of dinuclear zirconium and hafnium complexes under the same conditions. The much less activity is possibly explained by the steric repulsion from the POM frameworks in the dinuclear complexes. © 2008 American Chemical Society;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
Journal article (JA)
引用
收藏
页码：5472 / 5478
相关论文
共 50 条
  • [1] Synthesis and catalysis of di- and tetranuclear metal sandwich-type silicotungstates [(γ-SiW10O36)2M2(μ-OH)2]10- and [(γ-SiW10O36)2M4(μ4-O)(μ-OH)6]8- (M = Zr or Hf)
    Kikukawa, Yuji
    Yamaguchi, Syuhei
    Tsuchida, Kazutaka
    Nakagawa, Yoshinao
    Uehara, Kazuhiro
    Yamaguchi, Kazuya
    Mizuno, Noritaka
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (16) : 5472 - 5478
  • [2] Electrooxidation of Ethanol and Methanol Using the Molecular Catalyst [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]10-
    Liu, YuPing
    Zhao, Shu-Feng
    Guo, Si-Xuan
    Bond, Alan M.
    Zhang, Jie
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (08) : 2617 - 2628
  • [3] Synthesis and structure of asymmetric zirconium-substituted silicotungstates, [Zr6O2(OH)4(H2O)3(β-SiW10O37)3]14- and [Zr4O2(OH)2(H2O)4(β-SiW10O37)2]10-
    Bassil, BS
    Dickman, MH
    Kortz, U
    INORGANIC CHEMISTRY, 2006, 45 (06) : 2394 - 2396
  • [4] Graphene-supported [{Ru4O4(OH)2(H2O)4}-(γ-SiW10O36)2]10- for highly efficient electrocatalytic water oxidation
    Guo, Si-Xuan
    Liu, Yuping
    Lee, Chong-Yong
    Bond, Alan M.
    Zhang, Jie
    Geletii, Yurii V.
    Hill, Craig L.
    ENERGY & ENVIRONMENTAL SCIENCE, 2013, 6 (09) : 2654 - 2663
  • [5] Synthesis and structural characterization of a γ-Keggin-type dimeric silicotungstate with a bis(μ-hydroxo) dizirconium core [(γ-SiW10O36)2Zr2(μ-OH)2]10-
    Yamaguchi, Syuhei
    Kikukawa, Yuji
    Tsuchida, Kazutaka
    Nakagawa, Yoshinao
    Uehara, Kazuhiro
    Yamaguchi, Kazuya
    Mizuno, Noritaka
    INORGANIC CHEMISTRY, 2007, 46 (21) : 8502 - 8504
  • [6] Synthesis, characterization, and multielectron redox property of pyridine-coordinated tetra-Ru-oxo core sandwich-type silicotungstate, [(γ-SiW10O36)2({Ru(IV)(pyridine)}4O4(OH)2]10-
    Kokumai, Kodai
    Sugiarto
    Sadakane, Masahiro
    ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2022, 648 (13):
  • [7] Synthesis, crystal structure and electrochemical behavior of tetranuclear transition metal clusters based on lacunary silicotungstates:: [M4(H2O)2(SiW9O34)2]10- (M = Ni2+, Co2+) and [Fe4(μ-O)2(μ-OH)2(SiW10O37)2]14-
    Zhao, Xia
    Li, Yang-Guang
    Wang, Yong-Hui
    Wang, En-Bo
    TRANSITION METAL CHEMISTRY, 2008, 33 (03) : 323 - 330
  • [8] Synthesis, crystal structure and electrochemical behavior of tetranuclear transition metal clusters based on lacunary silicotungstates: [M4(H2O)2(SiW9O34)2]10− (M = Ni2+, Co2+) and [Fe4(μ-O)2(μ-OH)2(SiW10O37)2]14−
    Xia Zhao
    Yang-Guang Li
    Yong-Hui Wang
    En-Bo Wang
    Transition Metal Chemistry, 2008, 33 : 323 - 330
  • [9] Voltammetric Determination of the Reversible Potentials for [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]10- over the pH Range of 2-12: Electrolyte Dependence and Implications for Water Oxidation Catalysis
    Liu, Yuping
    Guo, Si-Xuan
    Bond, Alan M.
    Zhang, Jie
    Geletii, Yurii V.
    Hill, Craig L.
    INORGANIC CHEMISTRY, 2013, 52 (20) : 11986 - 11996
  • [10] Synthesis and characterization of sandwich rare earth metal monosubstituted polyoxometalates with γ-[SiW10O36]8- as ligand
    Yue, B
    Jiang, L
    Kong, ZP
    Jiao, F
    Lin, XR
    Jin, SL
    CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE, 2004, 25 (02): : 199 - 203
12345