Alpha and beta isomers of tetrahafnium(IV) containing decatungstosilicates, [Hf4(OH)6(CH3COO)2(x-SiW10O37)2]12- (x = α, β)

被引:23
作者
Assran, Awatef S. [1 ,3 ]
Mal, Sib Sankar [1 ,4 ]
Izarova, Natalya V. [1 ]
Banerjee, Abhishek [1 ]
Suchopar, Andreas [1 ]
Sadakane, Masahiro [2 ]
Kortz, Ulrich [1 ]
机构
[1] Jacobs Univ, Sch Engn & Sci, D-28725 Bremen, Germany
[2] Hiroshima Univ, Grad Sch Engn, Higashihiroshima 7398527, Japan
[3] S Valley Univ, Fac Sci Qena, Dept Chem, Qena 83523, Egypt
[4] Univ Ottawa, Ctr Catalysis Res & Innovat, Dept Chem, Ottawa, ON K1N 6N5, Canada
关键词
VIBRATIONAL INVESTIGATIONS; CRYSTAL-STRUCTURE; ZR-IV; HF-IV; KEGGIN; COMPLEXES; DAWSON; ZIRCONIUM; OXIDATION; POLYOXOMETALATE;
D O I
10.1039/c0dt01543a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The two dimeric, Hf-containing tungstosilicates [Hf-4(OH)(6)(CH3COO)(2)(alpha-SiW10O37)(2)](12)- (1) and [Hf-4(OH)(6)(CH3COO)(2)(beta-SiW10O37)(2)](12-) (2) have been synthesized by reacting HfCl4 with [gamma-SiW10O36](8-) in potassium acetate solutions at pH = 3.6 and 4.8, respectively. Polyanions 1 and 2 comprise a tetrahafnium(IV) assembly {Hf-4(OH)(6)(CH3COO)(2)} sandwiched between two dilacunary [alpha-SiW10O36](8-) (in 1) or {beta-SiW10} (in 2) Keggin type decatungstosilicates. This implies that the starting precursor {gamma-SiW10} isomerizes in situ to [beta-SiW10O37](10-) and then to [alpha-SiW10O37](10-) by controlled variation of pH and temperature. The hydrated potassium salts of 1 and 2 were investigated in the solid state by single-crystal XRD, FT-IR, thermogravimetric and elemental analyses, and in solution by UV-Vis and W-183 NMR spectroscopy, and electrochemistry.
引用
收藏
页码:2920 / 2925
页数:6
相关论文
共 65 条
[1]   Hexazirconium- and Hexahafnium-Containing Tungstoarsenates(III) and Their Oxidation Catalysis Properties [J].
Al-Kadamany, Ghada ;
Mal, Sib Sankar ;
Milev, Borislav ;
Donoeva, Baira G. ;
Maksimovskaya, Raisa I. ;
Kholdeeva, Oxana A. ;
Kortz, Ulrich .
CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (39) :11797-11800
[2]   Mechanistic Insights into Alkene Epoxidation with H2O2 by Ti-and other TM-Containing Polyoxometalates: Role of the Metal Nature and Coordination Environment [J].
Antonova, Nadya S. ;
Carbo, Jorge J. ;
Kortz, Ulrich ;
Kholdeeva, Oxana A. ;
Poblet, Josep M. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (21) :7488-7497
[3]   6-peroxo-6-zirconium crown and its hafnium analogue embedded in a. triangular polyanion:: [M6(O2)6(OH)6(γ-SiW10O36)3]18 (M = zr, hf) [J].
Bassil, Bassem S. ;
Mal, Sib Sankar ;
Dickman, Michael H. ;
Kortz, Ulrich ;
Oelrich, Holger ;
Walder, Lorenz .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (21) :6696-+
[4]   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- [J].
Bassil, BS ;
Dickman, MH ;
Kortz, U .
INORGANIC CHEMISTRY, 2006, 45 (06) :2394-2396
[5]   Increased Lewis acidity in hafnium-substituted polyoxotungstates [J].
Boglio, Cecile ;
Micoine, Kevin ;
Remy, Pauline ;
Hasenknopf, Bernold ;
Thorimbert, Serge ;
Lacote, Emmanuel ;
Malacria, Max ;
Afonso, Carlos ;
Tabet, Jean-Claude .
CHEMISTRY-A EUROPEAN JOURNAL, 2007, 13 (19) :5426-5432
[6]   Zirconium-substituted isopolytungstates: Structural models for zirconia-supported tungsten catalysts [J].
Carabineiro, H ;
Villanneau, R ;
Carrier, X ;
Herson, P ;
Lemos, F ;
Ribeiro, FR ;
Proust, A ;
Che, M .
INORGANIC CHEMISTRY, 2006, 45 (05) :1915-1923
[7]   COORDINATION CHEMISTRY OF SOLUBLE METAL-OXIDES OF MOLYBDENUM AND VANADIUM [J].
CHEN, Q ;
ZUBIETA, J .
COORDINATION CHEMISTRY REVIEWS, 1992, 114 (02) :107-167
[8]   Tetravalent metal complexation by Keggin and lacunary phosphomolybdate anions [J].
Copping, Roy ;
Jonasson, Leif ;
Gaunt, Andrew J. ;
Drennan, Dennis ;
Collison, David ;
Helliwell, Madeleine ;
Pirttijarvi, Ross J. ;
Jones, Chris J. ;
Huguett, Anne ;
Apperley, David C. ;
Kaltsoyannis, Nikolas ;
May, Iain .
INORGANIC CHEMISTRY, 2008, 47 (13) :5787-5798
[9]   METAL-OXIDE CHEMISTRY IN SOLUTION - THE EARLY TRANSITION-METAL POLYOXOANIONS [J].
DAY, VW ;
KLEMPERER, WG .
SCIENCE, 1985, 228 (4699) :533-541
[10]   Water Dissociation on α1-Hafnium and Ytterbium Substituted Dawson Polyoxotungstates: A Density Functional Theory Study [J].
Derat, Etienne ;
Lacote, Emmanuel ;
Hasenknopf, Bernold ;
Thorimbert, Serge ;
Malacria, Max .
JOURNAL OF PHYSICAL CHEMISTRY A, 2008, 112 (50) :13002-13005