IMMOBILIZATION OF THALLIUM BY TANDEM OXIDATION REDUCTION COMPLEXATION OF THALLIUM(I/III)

被引:36
作者
KAHWA, IA
MILLER, D
MITCHEL, M
FRONCZEK, FR
GOODRICH, RG
WILLIAMS, DJ
OMAHONEY, CA
SLAWIN, AMZ
LEY, SV
GROOMBRIDGE, CJ
机构
[1] IMPERIAL COLL SCI TECHNOL & MED,LONDON SW7 2AY,ENGLAND
[2] LOUISIANA STATE UNIV,DEPT PHYS,BATON ROUGE,LA 70803
[3] LOUISIANA STATE UNIV,BATON ROUGE,LA 70803
关键词
D O I
10.1021/ic00045a020
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Development of management procedures for toxic superconducting thallium-copper-alkaline earth ceramics and their byproducts requires better understanding of the complexometric chemistry of thallium in the presence of copper and alkaline earth cations. This study reveals that thallium can be immobilized as a thallium-rich mixed-valence solid[(Tl18c6)4CuCl4][TlCl4]2.nH2O(1, n = 0; 2, n = 0.25). When either Tl(I) or Tl(III) is treated with 18-crown-6 (18c6) in the presence of copper(II) (or zinc) chloride, tandem oxidation (or reduction) complexation occurs to an extent sufficient to form 1 and/or 2. The divalent transition metal ion (M) plays a beneficial role of concentrating Tl+ as a cation [(Tl18C6)4MCl4]2+, M = Cu or Zn. The template concerted reduction/oxidation-complexation reactions appear to take advantage of the high stability of the TlC14 anions. Similar complexes are obtained if Cl- is replaced by Br-, Tl+ by Rb+, and Cu2+ by Mn2+ and Co2+. The crystal structures of 1, 2, (Rb18c6)2Cu2Cl6 (5), and (Ba18c6)2(CuCl4)2-3H2O(6) along with solid-state thallium-205 NMR spectra of 1,2,[(Tl18c6)4ZnCl4][TlCl4]2 (3), and [(Rb18c6)4CuCl4][TlCl4]2 (4) are reported. The cubic (F23) complexes 1, 2, and 4 feature a room-temperature average T(d) geometry for CuCl42- anions, and the T(d) nature (required by symmetry) of the position it occupies is confirmed by the luminescence of T(d) MnCl42- and the blue color of T(d) CoCl42- ions substituting for CuCl42- species. Crystal data are as follows. 1: cubic, space group F23 with a = 20.728 (2) angstrom, V = 8905.1 (9) angstrom3, and Z = 4; with 661 reflections having I > 1-sigma(I), R = 0.038. 2: cubic, space group F23 with a = 20.748 (5) angstrom, V = 8932 angstrom3, Z = 4; with 549 independent reflections having \F(o)\ > 3-sigma(\F(o)\), R = 0.043. 5: monoclinic, space group P2(1)/c with a = 11.100 (2) angstrom, b = 8.168 (1) angstrom, c = 22.626 (5) angstrom, beta = 97.55 (2)-degrees, V = 2034 angstrom3, and Z = 2; with 2456 reflections (\F(o)\ > 3-sigma(\F(o)\)), R = 0.042. 6: triclinic P1BAR with a = 8.757 (3) angstrom, b = 17.174 (5) angstrom, c = 17.616 (6) angstrom, alpha = 66.23 (3)-degrees, beta = 77.31 (3)-degrees, gamma = 75.71 (2)-degrees, V = 2327.9 (13) angstrom, and Z = 2; using 6214 reflections (I > 3-sigma(I)), R = 0.051.
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页码:3963 / 3970
页数:8
相关论文
共 59 条
[1]  
ANDERSON DN, 1971, INORG CHIM ACTA, V5, P175
[2]   PREPARATION AND PROPERTIES OF BIS(ACETONITRILE)IODINE(I) HEXAFLUOROMOLYBDATE(V) AND HEXAFLUOROURANATE(V) [J].
ANDERSON, GM ;
WINFIELD, JM .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1986, (02) :337-341
[3]   SYNTHESIS AND SPECTROSCOPIC AND STRUCTURAL INVESTIGATION ON TETRAKIS(N-(2-AMMONIOETHYL)PIPERAZINIUM) DI-MU-CHLORO-DODECACHLOROTRICUPRATE(II) BIS(TETRACHLOROCUPRATE(II)), (C6H18N3)4CU5CL22 [J].
ANTOLINI, L ;
MARCOTRIGIANO, G ;
MENABUE, L ;
PELLACANI, GC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (17) :5506-5510
[4]   SPECTROSCOPIC AND STRUCTURAL INVESTIGATION ON THE PENTACHLORO-CUPRATE AND (MIXED-PENTAHALO) CUPRATE(II) OF THE N-(2-AMMONIUMETHYL)PIPERAZINIUM CATION - 1ST CASE OF MONOMERIC PENTAHALO-CUPRATE(II) HAVING SQUARE-PYRAMIDAL STRUCTURE - CRYSTAL AND MOLECULAR-STRUCTURE OF THE (N-(2-AMMONIUMETHYL)PIPERAZINIUM) PENTACHLORO-CUPRATE(II) DIHYDRATEOM [J].
ANTOLINI, L ;
MARCOTRIGIANO, G ;
MENABUE, L ;
PELLACANI, GC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (04) :1303-1309
[5]   ANISOTROPIC EXCHANGE IN TRANSITION-METAL DINUCLEAR COMPLEXES .6. BIS(MU-CHLORO)BIS(DICHLOROCUPRATES(II)) [J].
BENCINI, A ;
GATTESCHI, D ;
ZANCHINI, C .
INORGANIC CHEMISTRY, 1985, 24 (05) :704-708
[6]   THE CRYSTAL AND MOLECULAR-STRUCTURES OF [CO(NH3)6][CUCL5] AS DETERMINED FROM SINGLE-CRYSTAL X-RAY AND NEUTRON-DIFFRACTION DATA [J].
BERNAL, I ;
KORP, JD ;
SCHLEMPER, EO ;
HUSSAIN, MS .
POLYHEDRON, 1982, 1 (04) :365-369
[7]   PREPARATION OF SILICA GEL-BOUND MACROCYCLES AND THEIR CATION-BINDING PROPERTIES [J].
BRADSHAW, JS ;
BRUENING, RL ;
KRAKOWIAK, KE ;
TARBET, BJ ;
BRUENING, ML ;
IZATT, RM ;
CHRISTENSEN, JJ .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (12) :812-814
[8]  
CLAY RM, 1973, J CHEM SOC DALTON, P595, DOI 10.1039/dt9730000595
[9]   DISCRETE VARIATIONAL X-ALPHA CALCULATIONS OF THE SPECTRA OF CHLOROCUPRATE(II) COMPLEXES - A DETAILED COMPARISON WITH EXPERIMENT AND THE CELLULAR LIGAND-FIELD MODEL [J].
DEETH, RJ .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1990, (01) :355-363
[10]   DETAILED ABSORPTION, REFLECTANCE, AND UV PHOTOELECTRON SPECTROSCOPIC AND THEORETICAL-STUDIES OF THE CHARGE-TRANSFER TRANSITIONS OF CUCL42- - CORRELATION OF THE SQUARE-PLANAR AND THE TETRAHEDRAL LIMITS [J].
DESJARDINS, SR ;
PENFIELD, KW ;
COHEN, SL ;
MUSSELMAN, RL ;
SOLOMON, EI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (14) :4590-4603