Oxovanadium(IV)-sulfite compounds: Synthesis and structural and physical studies

被引:13
作者
Chilas, GI
Miras, HN
Manos, MJ
Woollins, JD
Slawin, AMZ
Stylianou, M
Keramidas, AD
Kabanos, TA [1 ]
机构
[1] Univ Ioannina, Dept Chem, Sect Inorgan & Analyt Chem, GR-45110 Ioannina, Greece
[2] Univ Cyprus, CY-1678 Nicosia, Cyprus
[3] Univ St Andrews, Dept Chem, St Andrews KY16 9AJ, Fife, Scotland
关键词
oxovanadium; sulfite; vanadium clusters; vanadium(IV); electrochemistry;
D O I
10.1351/pac200577091529
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Reaction of VIVOCl2 in strongly acidic aqueous solution with either (NH4)(2)SO3 or Na2SO3 and Bu4NBr at similar to 70 degrees C in the pH range 2.5-4.5 gives the clusters (NH4)(2){[V-4(IV)(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3)(4)O-4(H2O)(2)} and (n-Bu4N)(2){[V-4(IV)(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3)(4)O-4(H2O)(2)}, respectively. Reaction of (NH4VO3)-O-V with (NH4)(2)SO3 resulted in the isolation of the first compound. When the latter reaction is carried out in the presence of MgO, compound (NH4)[(VO)-O-IV(SO3)(1.5)H2O](infinity)center dot 2.5H(2)O was isolated instead. Compound (n-Bu4N)(2){[V-4(IV)(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3)(4)O-4(H2O)(2)} and (NH4)[(VO)-O-IV(SO3)(1.5)H2O](infinity)center dot 2.5H(2)O were characterized by X-ray structure analysis. The crystal structure of species (n-Bu4N)(2){IV4IV(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3)(4)O-4(H2O)(2)} revealed a unprecedented hexanuclear cluster consisting of a cubane core [M-4(mu(4)-O)(2)(mu(3)- OH)(2)] connected to two other metal atoms through the core oxo-groups and four mu(3)-SO3 bridges. Compound (NH4)[VIVO(SO3)(1.5)H2O](infinity)center dot 2.5H(2)O represents a rare example of an open-framework species prepared under mild conditions. Cyclic voltammetric examination of compound (n-Bu4N)(2){[IV4IV(mu(4)-O)(2)(mu(3)-OH)(2)]((VO)-O-IV)(2)(mu(3)-SO3)(4)O-4(H2O)(2)] revealed a redox process which was assigned to the oxidation of one core of vanadium(IV) to vanadium(V).
引用
收藏
页码:1529 / 1538
页数:10
相关论文
共 49 条
[1]  
[Anonymous], POLYOXOMETALATES PLA
[2]  
BAKER EN, 1978, PORPHYRINS, V1
[3]   Structural relationships, interconversion, and optical properties of the uranyl iodates, UO2(IO3)2 and UO2(IO3)2(H2O):: A comparison of reaactions under mild and supercritical conditions [J].
Bean, AC ;
Peper, SM ;
Albrecht-Schmitt, TE .
CHEMISTRY OF MATERIALS, 2001, 13 (04) :1266-1272
[4]   A new oxoanion:: [IO4]3- containing I(V) with a stereochemically active lone-pair in the silver uranyl iodate tetraoxoiodate(V), Ag4(UO2)4(IO3)2(IO4)2O2 [J].
Bean, AC ;
Campana, CF ;
Kwon, O ;
Albrecht-Schmitt, TE .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (36) :8806-8810
[5]   TRANSITION-METAL-CATALYZED OXIDATION OF SULFUR(IV) OXIDES - ATMOSPHERIC-RELEVANT PROCESSES AND MECHANISMS [J].
BRANDT, C ;
VANELDIK, R .
CHEMICAL REVIEWS, 1995, 95 (01) :119-190
[6]   Solid state coordination chemistry of oxomolybdenum organoarsonate materials [J].
Burkholder, E ;
Wright, S ;
Golub, V ;
O'Connor, CJ ;
Zubieta, J .
INORGANIC CHEMISTRY, 2003, 42 (23) :7460-7471
[7]   Solid state coordination chemistry: One-, two-, and three-dimensional materials constructed from molybdophosphonate subunits linked through binuclear copper tetra-2-pyridylpyrazine groups [J].
Burkholder, E ;
Golub, V ;
O'Connor, CJ ;
Zubieta, J .
INORGANIC CHEMISTRY, 2003, 42 (21) :6729-6740
[8]  
Cheetham AK, 1999, ANGEW CHEM INT EDIT, V38, P3268, DOI 10.1002/(SICI)1521-3773(19991115)38:22<3268::AID-ANIE3268>3.0.CO
[9]  
2-U
[10]   Magnetic clusters from polyoxometalate complexes [J].
Clemente-Juan, JM ;
Coronado, E .
COORDINATION CHEMISTRY REVIEWS, 1999, 193-5 :361-394