POLYOXO ALKOXIDES OF VANADIUM - THE STRUCTURES OF THE DECANUCLEAR VANADIUM(IV) CLUSTERS [V10O16(CH3CH2C(CH2O)3)4]4- AND [V10O13(CH3CH2C(CH2O)3)5]-

被引:81
作者
KHAN, MI
CHEN, Q
GOSHORN, DP
HOPE, H
PARKIN, S
ZUBIETA, J
机构
[1] SYRACUSE UNIV,DEPT CHEM,SYRACUSE,NY 13244
[2] UNIV CALIF DAVIS,DEPT CHEM,DAVIS,CA 95616
[3] EXXON RES & ENGN CO,ANNANDALE,NJ 08801
关键词
D O I
10.1021/ja00035a027
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The hydrothermal reaction of a mixture of vanadium oxides with CH3CH2C(CH2OH)3 in the presence of NH4Cl yields (NH4)4[V10O16{CH3CH2C(CH2O)3}4].4H2O (I). In contrast, the reaction of vanadium oxides with the same ligand, using Et4NCl as mineralizer, yields (Et4N)[V10O13{CH3CH2C(CH2O)3}5] (II). Both I and II exhibit structures based on the decavanadium core, {V10O28}. While 12 doubly and triply bridging oxo groups of the [V10O28]6- prototype are replaced by alkoxy oxygens of the ligands in I, 15 doubly and triply bridging oxo groups are replaced in II. In addition to the incorporation of alkoxy ligands into the {V10O28} core, I and II are unusual in that the vanadium sites exhibit the V(IV) oxidation state rather than V(V) as observed for the parent core. The relatively small structural distortions associated with this reduction of the core are noteworthy. Crystal data for (NH4)4[V10O16{CH3CH2C(CH2O)3}4].4H2O (I): space group, C2/c; a = 17.320 (2) angstrom; b = 24.904 (3) angstrom; c = 12.430 (2) angstrom; beta = 106.32 (1)-degrees; V = 5146 (3) angstrom 3; Z = 2; D(calc) = 1.840 g/cm3; structure solution and refinement based on 4053 reflections, R = 0.042. Crystal data for (Et4N)[V10O13{CH3CH2C(CH2O)3}5] (II): space group, P2(1)/c; a = 12.290 (2) angstrom; b = 19.115 (2) angstrom; c = 23.701 (4) angstrom; beta = 98.80 (1)-degrees; V = 5502 (2) angstrom 3; Z = 4; D(calc) = 1.815 g/cm3; 4436 reflections, R = 0.079. An analogous compound to II, (Me4N)2/3(Et4N)1/3[V10O13{CH3C(CH2O)3}5].0.69H2O (III) was prepared in a similar fashion. Crystal data for (Me4N)2/3(Et4N)1/3[V10O13{CH3C(CH2O)3}5].0.69H2O (III): space group, P2(1)/n; a = 12.235 (2) angstrom; b = 22.484 (6) angstrom; c = 53.439 (13) angstrom; beta = 92.61 (2)-degrees; V = 14685 (6) angstrom 3; Z = 12; D(calc) = 1.913 g/cm3; 11 994 reflections, R = 0.0851.
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页码:3341 / 3346
页数:6
相关论文
共 38 条
[1]   EMPIRICAL PARAMETERS FOR CALCULATING CATION-OXYGEN BOND VALENCES [J].
BROWN, ID ;
WU, KK .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1976, 32 (JUL15) :1957-1959
[2]   PROTONATION SITES IN THE DECAVANADATE ION - X-RAY CRYSTAL-STRUCTURE OF TETRAKISADENOSINIUM DIHYDRODECAVANADATE(V) UNDECAHYDRATE [J].
CAPPARELLI, MV ;
GOODGAME, DML ;
HAYMAN, PB ;
SKAPSKI, AC .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (10) :776-777
[3]  
Carlin R. L., 1986, MAGNETOCHEMISTRY
[4]   COORDINATION CHEMISTRY OF POLYOXOMOLYBDATES - THE STRUCTURE OF A DODECANUCLEAR MOLYBDATE CAGE INCORPORATING HYDROGEN SQUARATE LIGANDS, [(C4H9)4N]4[MO12O36(C4O4H)4].10ET2O [J].
CHEN, Q ;
LIU, SC ;
ZUBIETA, J .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1990, 29 (01) :70-72
[5]   A CYCLIC OCTANUCLEAR POLYOXOALKOXYVANADATE(IV) WITH AN OXALATE-BINDING CAVITY, [(N-C4H9)4N]2[V8O8(OCH3)16(C2O4)] - STRUCTURAL COMPARISON WITH THE ANALOGOUS POLYMOLYBDATE(V) COMPLEX [(N-C4H9)4N]2[MO8O16(OC2H5)8(C2O4)] [J].
CHEN, Q ;
LIU, SC ;
ZUBIETA, J .
INORGANIC CHEMISTRY, 1989, 28 (25) :4433-4434
[6]  
Chen Q., 1990, INORG CHEM, V29, P1458
[7]  
Chen Q., UNPUB
[8]   WHERE ARE THE PROTONS IN H3V10O283-? [J].
DAY, VW ;
KLEMPERER, WG ;
MALTBIE, DJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (10) :2991-3002
[9]   METAL-OXIDE CHEMISTRY IN SOLUTION - THE EARLY TRANSITION-METAL POLYOXOANIONS [J].
DAY, VW ;
KLEMPERER, WG .
SCIENCE, 1985, 228 (4699) :533-541
[10]   REINTERPRETATION OF 5 RECENT CRYSTAL-STRUCTURES OF HETEROPOLY AND ISOPOLY COMPLEXES - DIVANADODECAMOLYBDOPHOSPHATE, TRIVANADOENNEAMOLYBDOPHOSPHATE, GAMMA-DODECATUNGSTOPHOSPHATE, THE DODECAMOLYBDATE-DODECAMOLYBDOMOLYBDATE BLUE COMPLEX, AND DIHYDROGEN DECAVANADATE [J].
EVANS, HT ;
POPE, MT .
INORGANIC CHEMISTRY, 1984, 23 (04) :501-504