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Copper(I) complexes from CuX2(X = NO3, BF4, 1 2SO4) and some heterocyclic ligands containing the thioamido group
Complexes of copper(I) CuLnX(n = 2, 3; X = NO3, BF4 1 2SO4) have been obtained by reacting the corresponding copper(II) salts with the following ligands HNCH2·CH2X·C = S (where X = NH, NMe, NEt, S, O and CH2). All the ligands bind the metal through the thioketonic sulphur, as shown by the IR spectroscopy. The copper(I) seems always to realize a trigonal planar geometry both with three molecules of ligands and with two ligands and
Ahmed Hussein, F. A. Devillanova, F. Isaia, G. Verani Copper(I) complexes with N-methylbenzothiazole-2-thione and -2-selone. Transit. Metal Chem., 1985, 10, 368.
N-methylbenzothiazole-2-thione (bttme) and -2-selone (btseme) form complexes with CuX 2 (X=Cl, Br, NO 3, 1/2SO 4 or BF 4). The reaction, carried out in MeOH, produces complexes of copper(I), whose stoichiometry mainly depends on the ligand. Infrared evidence shows that the coordination occurs through the exo-sulphur and selenium atoms
F. Cristiani, F. Demartin, F. A. Devillanova, F. Isaia, V. Lippolis, G. Verani Spectroscopic studies of charge-transfer complexes of 1,4,7-trithiacyclononane with diiodine.
1,4,7-Trithiacyclononane ([9]aneS3) reacts with molecular diiodine in CH2Cl2 to form a 1:1 adduct. The formation constant and the thermodynamic parameters of this adduct have been determined by UV-visible spectra of several solutions at the temperatures of 15, 20, 25, 30, and 35-degrees-C. The C-13 NMR spectra show that adducts with higher ligand/diiodine molar ratios are formed. Two neutral charge-transfer molecular compounds having formula 2[9]aneS3 . 4I2 (I) and [9]aneS3 . 3I2 . (II) have been obtained as crystals. The crystals of I are triclinic (a = 8.498(2) angstrom, b = 13.984(4) angstrom, c = 14.898(6) angstrom, alpha = 65.57(2)degrees, beta = 89.19(2)degrees, gamma = 81.26(2)degrees, Z = 2, space group P1BAR; R = 0.025) and contain units formed by two [9]aneS3 molecules connected by a diiodine molecule; one [9]aneS3 binds two other diiodine molecules, while the second binds only one other diiodine molecule. The crystals of II are monoclinic (a = 13.810(2) angstrom, b = 9.829(4) angstrom, c = 16.198(6) angstrom, beta = 113.41(2)degrees, Z = 4, space group P2(1)/c; R = 0.019) and contain molecules of [9]aneS3 binding three diiodine molecules. FT-Raman spectra in the characteristic nu(I-I) region, carried out on the solid adducts, are discussed in comparison with the structural parameters
Investigation of the nonlinear absorption of dithiolene complexes in the pico- and nanosecond timescales using the Z-scan technique
Heterocyclic pentaatomic molecules containing thio- and seleno-amido groups: linear relationship between nS/nSe lone pair ionization energies and 1:1 adduct formation constants with diiodine
Copper(I) complexes of pentatomic heterocyclic selone donors.
New complexes of copper(I) with some heterocyclic pentatomic rings, X·CH2·CH2·NR·CSe, where X=CH2, NH, NMe, NEt, S and R=H, Me, Et, were prepared by reacting copper(II) chloride and bromide in MeOH. The stoichiometry of the complexes and the binding mode of the ligands have been discussed comparatively, together with those of the thione parents. It is noteworthy that the selone ligands with R=H (L) yield complexes of the type CuLnY, (n=1,2 or 3; Y=Cl or Br) like the corresponding thione ones. On the contrary, when R=Me or Et, the selonic ligands (L′) give complexes whose stoichiometries, Cu2L′Y2 and Cu3L′2Y3, differ from the thione homologues. The i.r. spectra of the complexes compared with those of the ligands support the coordinative bond via selenium atom
Synthesis and crystal stucture of Tetrakis(N-methylbenzothiazole-2(3H)-selone)selenium(2+) tetrafluoroborate: the first example of cation containing the mixed-valence Se5 framework
A C-13 NMR study of 3,5,5-trimethyl-4-oxo-imidazolidine-2-thione and 3,5,5-trimethylimidazolidine-2,4- dithione complexes with molecular diiodine.
The C-13 NMR spectra of C.T. complexes between donors containing a thioamido group and diiodine are reported. The rapid exchange of donor between the free and the adduct state makes the variation in the position of the resonance depend on the ratio of these two species.
Data are comparatively examined with those of the related molecules: 5,5-dimethyl-4-oxoimidazolidine-2-thione and 5,5-dimethylimidazolidine-2,4-dithione. The influence of diiodine on the C-13 chemical shifts shows that I2 affects C(2) more than C(4) and confirms that, in the two compounds with two C=S groups, the interaction of I2 takes place with the sulphur bonded to C(2)
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