STRUCTURAL AND SPECTROSCOPIC FEATURES OF THE ADAMANTANE TYPE CU4S6 CORE FOUND IN CU(I) THIOLATES WITH BIDENTATE CHELATE LIGANDS

被引:16
作者
BAUMGARTNER, M
SCHMALLE, H
DUBLER, E
机构
[1] Institute of Inorganic Chemistry, University of Zürich, CH-8057 Zurich
关键词
D O I
10.1016/S0020-1693(00)85113-0
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Six tetranuclear Cu(I) thiolate complexes have been synthesized with the bidentate thiolate ligands dithioethane (DTE) and dithiopropane (DTP). The cell dimensions are a = 10.887(3), b = 12.294(6), c = 22.308(3) angstrom, alpha = 96.94(2), beta = 96.66(l), gamma = 108.57(3)-degrees, space group = P1BAR and V = 2772 angstrom3 for [(C6H5)4P+]2[Cu4(DTP2-)3] (A); a = 11.820(6), b = 13.972(5), c = 21.371(6) angstrom, alpha = 71.83(2), beta = 77.01(3), gamma = 63.61(4)-degrees, space group = P1BAR and V = 2988 angstrom3 for [(C6H5)4P+]2[CU4(DTP2-)3].3MeOH (B); a = 9.779(3), b = 9.779(4), c = 17.694(6) angstrom, alpha = 90.0, beta = 90.0, gamma = 120.0-degrees, space group = P6(3) and V = 1465 angstrom3 for [(CH3)4N+]2[Cu4(DTP2-)3].MeOH (C); a = 15.835(3), b = 20.413(4), c = 9.866(1) angstrom, alpha = 90.0, beta = 91.05(l), gamma = 90.0-degrees, space group = P2(1)/n and V = 3188 angstrom3 for [(C2H5)4N+]2[Cu4(DTE2-)3] (D); a = 9.939(5), b = 9.939(8), c = 34.201(7) angstrom, alpha = 90.0, beta = 90.0, gamma = 90.0-degrees, tetragonal, V = 3378 angstrom3 for [C6H5CH2N+(CH3)3]2[Cu4(DTE2-)3] (E) and a = 10.899(2), b = 10.879(2), c = 18.604(3) angstrom, alpha = 90.0, beta = 90.0, gamma = 120.0-degrees, hexagonal, V = 1913 angstrom3 for [(C2H5)4N+]2[CU4(DTP2-)3].MeOH (F). The structures were refined to R/R(w) values (%) of 6.75/5.63, 4.60/5.70, 6.56/7.42 and 5.59/5.35 for A-D, respectively. All compounds exhibit an anionic 'adamantane' type Cu4S6 cluster unit. Within two of the structures, inserted solvent molecules are linked with the Cu-S core by S ... H-O hydrogen bonds. Crystallization of the anionic [Cu4(RS-)6]2- or [Cu4(-SRS-)3]2-units together with bulky ammonium cations yields white or pale yellow compounds, whereas yellow, orange or deep red crystals are formed using the (C6H5)4P+ cation as the counterion. A review of IR data of different [Cu4(RS-)6]2- or [Cu4(-SRS-)3]2- is given.
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页码:135 / 143
页数:9
相关论文
共 48 条
[1]   SYNTHESIS, CHARACTERIZATION AND CRYSTAL-STRUCTURE OF COPPER(I) THIOLATES - [(C6H5)4P+]2[CU4(C2H5S-)6].0.5C2H6O2 AND [(C6H5)4P+][CU7(C2H5S-)8] [J].
BAUMGARTNER, M ;
SCHMALLE, H ;
DUBLER, E .
POLYHEDRON, 1990, 9 (09) :1155-1164
[2]   THERMAL-DEGRADATION OF COPPER(I) THIOLATE CLUSTERS AND THE CRYSTAL-STRUCTURE OF SOLVENT-FREE (PH4P)2[CU4(SPH)6] [J].
BAUMGARTNER, M ;
BENSCH, W ;
HUG, P ;
DUBLER, E .
INORGANICA CHIMICA ACTA-BIOINORGANIC CHEMISTRY, 1987, 136 (03) :139-147
[3]  
BAUMGARTNER M, 1993, IN PRESS SOLID STATE
[4]  
BAUMGARTNER M, IN PRESS J INORG BIO
[5]  
BAUMGARTNER M, 1990, THESIS U ZURICH SWIT
[6]   PRIMARY STRUCTURE AND SPECTROSCOPIC STUDIES OF NEUROSPORA COPPER METALLOTHIONEIN [J].
BELTRAMINI, M ;
LERCH, K .
ENVIRONMENTAL HEALTH PERSPECTIVES, 1986, 65 :21-27
[7]   SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF [CU(SC6H4-O-SIME3)]12, AN UNUSUAL EXAMPLE OF A PADDLE-WHEEL DODECAMETALLIC THIOLATE CLUSTER [J].
BLOCK, E ;
GERNON, M ;
KANG, H ;
LIU, SC ;
ZUBIETA, J .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (15) :1031-1033
[8]   COORDINATION CHEMISTRY OF STERICALLY HINDERED THIOLATE LIGANDS - PREPARATION AND STRUCTURAL CHARACTERIZATION OF THE OLIGOMERIC HOMOLEPTIC COMPLEXES [CU(SC6H4-ORTHO-SIME3)]12 AND [(AG(SC6H4-ORTHO-SIME3))4]2 AND A COMPARISON TO THE STRUCTURE OF THE MONONUCLEAR SPECIES (ET4N)2[CD(SC6H4-ORTHO-SIME3)4] [J].
BLOCK, E ;
GERNON, M ;
KANG, HK ;
OFORIOKAI, G ;
ZUBIETA, J .
INORGANIC CHEMISTRY, 1989, 28 (07) :1263-1271
[9]   PREPARATION AND LOW-FREQUENCY VIBRATIONAL-SPECTRA OF SOME COPPER(I) AND SILVER(I) ALKANE-MONOTHIOLATE AND ARENE-MONOTHIOLATE COMPLEXES [J].
BOWMAKER, GA ;
TAN, LC .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1979, 32 (07) :1443-1452
[10]   THE FORMATION AND STRUCTURAL CHEMISTRY OF THE HEXA(MU-TERT-BUTYLTHIOLATO) PENTACUPRATE(I) CAGE ANION WITH TRIETHYLAMMONIUM AND TETRAETHYLAMMONIUM CATIONS [J].
BOWMAKER, GA ;
CLARK, GR ;
SEADON, JK ;
DANCE, IG .
POLYHEDRON, 1984, 3 (05) :535-544