SYNTHESIS AND CHARACTERIZATION OF THE COMPLEXES [CU(II)(ET4TODIT)X2]N.NTHF (ET4TODIT=4,5,6,7-TETRATHIOCINO[1,2-B-3,4-B']-DIIMIDAZOLYL-1,3,8,10-TETRAETHYL-2,9-DITHIONE X = CL, BR) - CRYSTAL AND MOLECULAR-STRUCTURE OF [CU(II)(ET4TODIT)CL2]N.NTHF

被引:13
作者
BIGOLI, F
PELLINGHELLI, MA
DEPLANO, P
TROGU, EF
SABATINI, A
VACCA, A
机构
[1] UNIV CAGLIARI,DIPARTIMENTO CHIM & TECNOL INORGAN & MET ORGAN,VIA OSPED 72,I-09124 CAGLIARI,ITALY
[2] UNIV PARMA,CNR,CTR STUDIO STRUTTURIST DIFFRATTOMETR,IST CHIM GEN & INORGAN,I-43100 PARMA,ITALY
[3] UNIV FLORENCE,DIPARTIMENTO CHIM,I-50144 FLORENCE,ITALY
关键词
D O I
10.1016/S0020-1693(00)84933-6
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
By reacting CuX2 (X = Cl or Br) with Et4todit (Et4todit = the title ligand) in THF, the new ligand-bridged polynuclear complexes [Cu(II)(Et4todit)X2]n.nTHF have been obtained. The X-ray crystallographic studies on the Cl derivative show that the compound crystallizes in the orthorhombic space group Fdd2, with a = 32.674(6), b = 34.547(6), c = 10.162(3) angstrom, Z = 16. The coordination around the metal involves two Cl- ions and two S-thioamide atoms of two ligand molecules related by a screw axis, and is nearer to a square planar than to a tetrahedral arrangement. The bridging ligands form helical chains running parallel to c. The copper-copper distances in and between the chains are 7.601(4) and 9.185(5) angstrom, respectively. ESR measurements on this polymer give g values in accordance with a strongly distorted rhombic structure. The magnetic susceptibility data within the temperature range 5-150 K exhibit a Curie behaviour for both complexes (mu = 1.82 and 1.72 BM for Cl and Br complexes, respectively). Electronic spectroscopic results show that: (i) the environment around the copper(II) is the same in the solid state and in THF solution; (ii) reagents and products exist in THF at supersaturation conditions; (iii) S-(thioamide)copper(II) LMCT bands are observed at 555 and 620 nm for Cl and Br complexes, respectively. IR spectra agree with the X-ray structural results.
引用
收藏
页码:201 / 207
页数:7
相关论文
共 25 条
[1]   SULFUR-LIGAND-METAL COMPLEXES .4. COPPER-COMPLEXES WITH BIDENTATE TERTIARY-PHOSPHINE SULFIDE AND SELENIDE LIGANDS AND CRYSTAL-STRUCTURE OF A 3-CO-ORDINATE COPPER(1) COMPLEX [J].
AINSCOUGH, EW ;
BERGEN, HA ;
BRODIE, AM ;
BROWN, KA .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1976, (17) :1649-1656
[2]  
[Anonymous], 1974, INT TABLES XRAY CRYS, VIV, p[99, 149]
[3]   INTERACTION OF DIIODINE WITH SOME TETRA-SUBSTITUTED DITHIOOXAMIDES - CRYSTAL AND MOLECULAR-STRUCTURE OF BIS(MORPHOLINOTHIOCARBONYL)BIS(DIIODINE) [J].
ATZEI, D ;
DEPLANO, P ;
TROGU, EF ;
BIGOLI, F ;
PELLINGHELLI, MA ;
VACCA, A .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1988, 66 (06) :1483-1489
[4]   INTERACTION OF DIIODINE WITH ET4TODIT = 4,5,6,7-TETRATHIOCINO [1,2-B-3,4-B']DIIMIDAZOLYL-1,3,8,10-TETRAETHYL-2,9-DITHIONE - CRYSTAL AND MOLECULAR-STRUCTURE OF ET4TODIT.2I2 [J].
ATZEI, D ;
DEPLANO, P ;
TROGU, EF ;
BIGOLI, F ;
PELLINGHELLI, MA ;
SABATINI, A ;
VACCA, A .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1989, 67 (09) :1416-1420
[5]  
ATZEI D, 1988, PHOSPHORUS SULFUR, V37, P189
[6]   REACTION OF BIS(MORPHOLINOTHIOCARBONYL) DISULFIDE WITH IODINE - EXISTENCE OF A 1-1 CHARGE-TRANSFER PRECURSORY ADDUCT IN AN OXIDATION REACTION - ISOLATION AND CRYSTAL-STRUCTURE OF BIS[3,5-DI(N-MORPHOLINIO)-1,2,4-TRITHIOLANE] HEXADECAIODIDE [J].
BIGOLI, F ;
PELLINGHELLI, MA ;
CRISPONI, G ;
DEPLANO, P ;
TROGU, EF .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1985, (07) :1349-1353
[7]   COMPLEXES OF 4,5,6,7-TETRATHIOCINO[1,2-B-3,4-B']DIIMIDAZOLYL-1,3,8,10-TETRAETHYL-2,9-DITHIONE (ET4TODIT) WITH GROUP IIB METAL-HALIDES - CRYSTAL AND MOLECULAR-STRUCTURE OF (CD(II)ET4TODITCL2)N [J].
BIGOLI, F ;
PELLINGHELLI, MA ;
DEPLANO, P ;
TROGU, EF .
INORGANICA CHIMICA ACTA, 1990, 170 (02) :245-249
[8]   REACTION OF BIS(MORPHOLINOSELENOCARBONYL) TRISELENIDE WITH IODINE - EXISTENCE OF A 1-1 CHARGE-TRANSFER PRECURSORY ADDUCT IN SOLUTION IN AN OXIDATIVE REACTION - ISOLATION AND CRYSTAL-STRUCTURE OF THE NEW (N-MORPHOLINECARBODISELENOATO)SELENIUM(II) IODIDE [J].
BIGOLI, F ;
LEPORATI, E ;
PELLINGHELLI, MA ;
CRISPONI, G ;
DEPLANO, P ;
TROGU, EF .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1983, (08) :1763-1769
[9]  
BIGOLI F, 1987, J CHEM SOC DA, P2407
[10]   ADDUCT FORMATION OF TRIS(MORPHOLINE-4-CARBO-DITHIO OR DISELENOATO)CO(III) COMPLEXES WITH IODINE [J].
CRISPONI, G ;
DEPLANO, P ;
TROGU, EF .
INORGANICA CHIMICA ACTA-ARTICLES, 1983, 75 (01) :135-138