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1.
M. Sakhawat Hussain Abdul Rahman Al-Arfaj M. Latif Hossain 《Transition Metal Chemistry》1990,15(4):264-269
Summary Novel mixed-ligand copper(I) complexes of general formula [TPP–Cu–(L)Cl] or [TPPhos–Cu–(L)Cl], where TPP=triphenylphosphine, TPPhos=triphenylphosphate and L=imidazolidine-2-thione [Imt],N-propylimidazolidice-2-thione [PrImt],N-i-propylimidazolidine-2-thione [iPrImt], and 1,3-diazinine-2-thione [Diaz] and bis coniplexes of formula [(L)2CuCl] where L=[PrImt] and [iPrImt] have been prepared and characterized by electronic, vibrational and n.m.r. spectroscopy. The spectral data are consistent with S-donation of thiones. The magnitude of upfield shift in13Cn.m.r. of the thionreide carbon on complexation has been interpreted in terms of coordination geometry around the metal stoms. X-ray structure analysis agrees with the conclusions from the spectroscopic measurements. The structure of [(PrImt)2CuCl] revealed three-coordinated copper(I) with crystal data:a=14.106(4),b=14.380(2),c=19.024(3) A, =108.8(2)°,z=8 and space group P2/c. 相似文献
2.
P. Aslanidis V. Gaki K. Chrissafis M. Lalia-Kantouri 《Journal of Thermal Analysis and Calorimetry》2011,103(2):525-531
Copper(I) halide complexes formulated as [(L)CuX(μ2-L)2CuX(L)] (X = Cl, Br and L = pyridine-2-thione (py2SH), or 4,6-dimethylpyrimidine-2-thione (dmpymtH)) were prepared, and their
photoluminescence and thermal properties were investigated. The complexes are strongly emissive in the solid state, with the
emissions being dominated by large Stokes shifts (>200 nm), which are depending on both the heterocyclic thione and the nature
of the halogen. These emissions can be assigned to MLCT with some mixing of the halide-to-ligand (XL) CT characters. Simultaneous
TG/DTG–DTA technique, coupled with MS for the analysis of the gaseous decomposition products, was used for two complexes with
the dmpymtH ligand to determine their thermal degradation, which was found to be very complicated. In inert atmosphere the
residues at 1,000 °C (verified with PXRD) were a mixture of Cu2S and CuX, while at 1,300 °C a mixture of Cu2S and Cu. In oxygen atmosphere the residues were CuO. 相似文献
3.
Two series of copper (I) halide complexes formulated as [(L)CuX(μ2-L)2CuX(L)] and [(L)2Cu(μ2-L)2Cu(L)2]2+ 2Χ−, respectively (X = Cl, Br and L = 4,6-dimethylpyrimidine-2-thione (dmpymtH)) were prepared. From the thermogravimetric curves
it was found that among the four studied materials, [Cu2(dmpymtH)6]2+2Cl− presents a lower thermal stability. For the determination of the activation energy (E) two different methods have been used comparatively, since every method has its own error. These methods were the isoconversional
methods of Ozawa, Flynn and Wall (OFW), and Friedman. The dependence of the E on the value of the mass conversion α, as calculated with OFW and Friedman’s methods, can be separated in three distinct regions. The decomposition mechanism is
very complex and can be described using at least three different mechanisms with different activation energies. The best fitting
of experimental data with theoretical models gave nth-order for all the three mechanisms (Fn–Fn–Fn). 相似文献
4.
M. Sakhawat Hussain M. Latif Hossain Abderehman Al-Arfaj 《Transition Metal Chemistry》1990,15(2):120-125
Summary Novel mixed-ligand complexes of Ag1 and Au1 containing triphenylphosphine (TPP) and heterocyclic thiones, of general formula [TPP–M–L]Cl and [(TPP)2–M–L]Cl, where L=imidazolidine-2-thione (Imt), 1,3-diazinine-2-thione (Diaz) or N-isopropylimidazolidine-2-thione (iPrImt) have been prepared. The spectroscopic data are consistent with S-donation in all complexes. The magnitude of high-field shift in carbon-13 n.m.r. of the thioureide carbon on complexation is interpreted in terms of coordination geometry around the metal atoms. The mixed-ligand complexes are structurally similar to some of the commonly used antiarthritic Au1 drugs and are thus potentially useful in chemotherapy. 相似文献
5.
The reactions of mercury(II) halides with the tetraphosphinitoresorcinarene complexes [P4M5X5], where M=Cu or Ag, X=Cl, Br, or I, and P4=(PhCH2CH2CHC6H2)4(O2CR)4(OPPh2)4 with R=C6H11, 4-C6H4Me, C4H3S, OCH2CCH, or OCH2Ph, have been studied. The reactions of the complexes with HgX2 when M=Ag and X=Cl or Br occur with elimination of silver(I) halide and formation of [P4Ag2X(HgX3)], but when M=Ag and X=I, the complexes [P4Ag4I5(HgI)] are formed. When M=Cu and X=I, the products were the remarkable capsule complexes [(P4Cu2I)2(Hg2X6)]. When M=Ag and X=I, the reaction with both CuI and HgI2 gave the complexes [P4Cu2I(Hg2I5)]. Many of these complexes are structurally characterized as containing mercurate anions weakly bonded to cationic tetraphosphinitoresorcinarene complexes of copper(I) or silver(I) in an unusual form of host-guest interaction. In contrast, the complex [P4Ag4I5(HgI)] is considered to be derived from an anionic silver cluster with an iodomercury(II) cation. Fluxionality of the complexes in solution is interpreted in terms of easy, reversible making and breaking of secondary bonds between the copper(I) or silver(I) cations and the mercurate anions. 相似文献
6.
Reaction of copper(I) chloride or bromide with equimolar amounts of the neutral pyrimidine-2-thione ligand (pymtH) afforded linear chain polymers [Cu(pymtH)X]n (X = Cl, Br) with the pymtH ligand acting as a bridging N, S donor. In contrast, copper(I) iodide under the same conditions gave the dimeric complex [Cu(pymtH)2I]2 with the pymtH ligand adopting monodentate coordination mode through the exocyclic sulfur atom in terminal and bridging modes. Reactions of the heterocyclic thione ligand 2,4,6-trimercaptotriazine (H3TMT) with copper(I) halides afforded novel three-dimensional polymers, which crystallized in the cubic space group Pa. Each copper(I) ion is coordinated by three S atoms of three distinct H3TMT ligands, and each H3TMT acts as a tridentate bridging ligand linking three copper(I) ions through its sulfur atoms, thus forming two independent three-dimensional (3D) networks. The network belongs to a three-connected (10, 3)-a topology, which is enantiometric and interpenetrating. In all complexes the ligands are present in the thione form, and all halides are terminally coordinated to copper(I) ions. The photoluminescent and thermal properties of the complexes have also been investigated. 相似文献
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8.
Esther Hrmann Pascale C. Riesen Markus Neuburger Margareta Zehnder Thomas A. Kaden 《Helvetica chimica acta》1996,79(1):235-243
Three N2S2 macrocycles ( 3, 10, 12 ) carrying an amino group as a pendant arm have been synthesized and their complexation properties towards Ni2+ and Cu2+ studied. The crystal structures of the Cu2+ complexes with 10-methyl-1,4-dithia-7,10-diazacyclododecane-7-ethanamine ( 3 ) and 11-methyl-1,4-dithia-8,11-diazacyclotetradecane-8-ethanamine ( 10 ) show that, in both cases, the Cu2+ is pentacoordinated by the four donor atoms of the macrocycle and the amino group of the side chain. In aqueous solution, however, two forms of the complexes with stoichiometries [MLH] and [ML] (M = Cu2+ or Ni2+) have been observed. In [MLH], the amino group is protonated and does not bind to the metal ion, whereas in [ML] the amino group is bound, and a pentacoordinated geometry results. The pKa values for the equilibrium [ML] + H+?[MLH]+ decrease in the order 12 > 10 > 3 , indicating that the 2-aminoethyl side chain binds better to the Cu2+ than the 3-aminopropyl side chain. Cyclic voltammetry for the Cu2+/Cu+ pair shows that the 2-aminoethyl pendant arm stabilizes the Cu2+ oxidation state, when the metal ion is in the 14-membered ring ( 10 ), whereas it stabilizes Cu+ for the 12-membered macrocycle ( 3 ). 相似文献
9.
《Journal of organometallic chemistry》1986,303(1):C21-C24
Treatment of the coordinatively unsaturated cationic complexes, [(η-C3H5)(Ph3P)2PdII]PF6 and [(1,5-COD)2RhI]BF4, with potassium t-butylperoxide in dichloromethane gives the t-butylperoxometal complexes; (η-C3H5)(Ph3P)(t-BuOO)PdII and [(1,5-COD)(t-BuOO)RhI](KBF4), via nucleophilic attack by t-BuOO− on the cationic metal center. 相似文献
10.
Köhn RD Pan Z Haufe M Kociok-Köhn G 《Dalton transactions (Cambridge, England : 2003)》2005,(16):2793-2797
As the first 1st-row transition metal complexes having six tertiary amine donor groups, bis(triazacyclohexane) sandwich complexes [L2M](BF4)2 (L = benzyl- or p-fluorobenzyl-triazacyclohexane, M = Cu or Zn) have been obtained by the protonolysis of Et2Zn in the presence of L or by reaction of [Cu(MeCN)4](BF4) with L in CH2Cl2 and subsequent air oxidation via an unprecedented Cu(I)(2) sandwich complex containing a short Cu-Cu contact. 相似文献
11.
Azucena García-Onrubia Pilar Souza José R. Masaguer Agueda Arquero 《Transition Metal Chemistry》1988,13(5):384-387
Summary Copper(II) salts react with benzenecarbothioamide(BCTA);N,N-dimethylbencenecarbothioamide (DMBCTA) andN,N-diethylbenzenecarbothioamide (DEBCTA) to give complexes with 11, 21, 31 ligand/metal stoichiometric ratios, and a diamagnetic complex [Cu2(DEBCTA)Br4]2 which appears to contains copper(I). These compounds were characterized by elemental analyses, conductivities measurements, i.r., electronic and e.p.r. studies and magnetic measurements.The results suggest tetrahedral geometry for the copper(II) complexes, a dimeric structure for bromide-DMBCTA and chloride and bromide-BCTA derivatives, and a square pyramid geometry for the CuBr2-DEBCTA complex. No information is yet available on the coordination geometry of the copper(I) complex. 相似文献
12.
Thomas G. Ribelli Krzysztof Matyjaszewski 《Journal of Coordination Chemistry》2018,71(11-13):1641-1668
AbstractAlthough alkylcopper(I) reagents are widespread, compounds containing alkyl ligands on CuII or CuIII are much less common. Such complexes, however, are generated as transient species when carbon-center radicals add to CuI or CuII complexes, respectively, and appear to be involved in several copper-catalyzed organic transformations. A few organocopper(II) and organocopper(III) complexes were found sufficiently robust to allow isolation and full characterization. This article reviews the reactivity of carbon-centered radicals with CuI and CuII ions, both in aqueous and non-aqueous environments, with focus on the importance of the resulting organocopper species on atom transfer radical polymerization and on copper-catalyzed radical termination. 相似文献
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15.
《Journal of Coordination Chemistry》2012,65(16-18):2510-2525
AbstractTwo triply-bridged dinuclear copper(II) complexes of formula [LCu(μ-OH)(μ-OAc)(μ-X)CuL]X?0.5H2O where L is a bidentate ligand of N-(pyridine-2-ylmethyl)propane-2-amine and X=Cl, 1 and Br, 2 were synthesized and characterized by elemental analyses, spectroscopic techniques (IR, UV–Vis, EPR), thermal analysis, conductance measurements, and single-crystal X-ray structure determination. The structures of both complexes are similar. The complexes show a distorted square-pyramidal arrangement around each copper(II) ion with a CuN2O2X chromophore in which both copper(II) ions are connected by a hydroxo bridge and a triatomic syn-syn carboxylato bridge in equatorial positions and a halide ion bridge at the axial site. The chromotropism behavior of the complexes, including solvato-, thermo-, and halochromism, were investigated in detail. Their halochromism was investigated in the pH range of 2.0–11.0 by visible absorption spectroscopy. The reversible color variations from blue to colorless are attributable to deprotonation and protonation of the ligands. The complexes show reversible thermochromism in solution due to dissociation and recombination of ligands to copper ions. 相似文献
16.
Summary The rhodium(I) carbonyl compounds [Rh(CO)L22] [BF4]. 1/2CH2Clnn2 (L = PPh2 or AsPh3) react with the nucleophiles OMe−, RCOO− (R = Me, Et) under nitrogen to form [Rh(OR)(CO)L2] (1)–(2) and [Rh(OOCR)(CO)L2] (7)–(10), respectively. Addition of [Rh(CO)2(PPh3)2]-[BF 4] to OMe− under nitrogen produces [Rh(COOMe)-(CO) (PPh3)2]-MeOH (3), whilst reactions of [Rh(CO)-(PPh3)2] [BF4]·1/2CH2Cl2 and [Rh(CO)2(PPh3)2] [BF4] with OR- (R = Me, Et or n-Pr) in the presence of CO produce [Rh(COOR)(CO)2(PPh3)2] (4)–(6). The products have been characterised by i.r., 1H, 31P, 13Cn.m.r. spectroscopy and elemental analysis. 相似文献
17.
E. V. Malova T. V. Troepol'skaya G. N. Nikonov A. A. Karasik 《Russian Chemical Bulletin》1991,40(2):303-306
P-, B-, and O-containing compounds and their complexes with copper(I) in aprotic solvents were studied for the first time by electrochemical methods (classical polarography, millicoulometry, cyclic voltammetry, and electrolysis at controlled potential). A scheme of electroreduction of dioxaboraphosphorinanes on a dropping mercury electrode is suggested, the first step of which consists of cleavage of the P-C bond, accompanied by chemical reactions. It was discovered that the electrochemical reduction of copper complexes of 1,3,2,5-dioxaboraphosphorinanes occurs with accepting of the first electrons on the lower vacant molecular orbital, determined chiefly by the ligand and not by the metal ion.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 358–361, February, 1991.The authors would like to express gratitude to S. A. Flegontov and V. G. Malaev for performing the electrolysis at controlled potential. 相似文献
18.
Rojas D García AM Vega A Moreno Y Venegas-Yazigi D Garland MT Manzur J 《Inorganic chemistry》2004,43(20):6324-6330
The bis-pyridine tridentate ligands (6-R-2-pyridylmethyl)-(2-pyridylmethyl) benzylamine (RDPMA, where R = CH(3), CF(3)), (6-R-2-pyridylmethyl)-(2-pyridylethyl) benzylamine (RPMPEA, where R = CH(3), CF(3)), and the bidentate ligand di-benzyl-(6-methyl-2-pyridylmethyl)amine (BiBzMePMA) have been synthesized and their copper(I) complexes oxidized in a methanol solution to afford self-assembled bis-micro-methoxo-binuclear copper(II) complexes (1, 2, 4, 6) or hydroxo- binuclear copper(II) complexes (3). Oxidation of the nonsubstituted DPMA (R = H) in dichloromethane gives a chloride-bridged complex (5). The crystal structures for [Cu(MeDPMA)(MeO)](2)(ClO(4))(2) (1), [Cu(RPMPEA)(MeO)](2)(ClO(4))(2) (for 2, R= Me, and for 4, R = CF(3)), [Cu(BiBzMePMA)(MeO)](2)(ClO(4))(2) (6), [Cu(FDPMA)(OH)](2)(ClO(4))(2) (3), and [Cu(DPMA)(Cl)](2)(ClO(4))(2) (5) have been determined, and their variable-temperature magnetic susceptibility has been measured in the temperature range of 10-300 K. The copper coordination geometries are best described as square pyramidal, except for 6, which is square planar, because of the lack of one pyridine ring in the bidentate ligand. In 1-4 and 6, the basal plane is formed by two pyridine N atoms and two O atoms from the bridging methoxo or hydroxo groups, whereas in 5, the bridging Cl atoms occupy axial-equatorial sites. Magnetic susceptibility measurements show that the Cu atoms are strongly coupled antiferromagnetically in the bis-methoxo complexes 1, 2, 4, and 6, with -2J > 600 cm(-)(1), whereas for the hydroxo complex 3, -2J = 195 cm(-)(1) and the chloride-bridged complex 5 shows a weak ferromagnetic coupling, with 2J = 21 cm(-)(1) (2J is an indicator of the magnetic interaction between the Cu centers). 相似文献
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20.
Enthalpies of the decomposition reactions MX2L2(c)→MX2(c) + 2L (g), where M is Mn, Co, Ni, Cu, or Cd, X is Cl and/or Br, and L is benzothiazole or 2-methyl-benzothiazole have been measured by use of a differential scanning calorimeter. Specific heats and enthalpies of sublimation of some of the complexes have been obtained. 相似文献