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1.
Nirmal K. Shee F.A. Oluwafunmilayo Adekunle Michael G.B. Drew 《Inorganica chimica acta》2011,366(1):198-202
Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Cu(ClO4)2·6H2O in methanol in 3:1 M ratio at room temperature yields light green [CuL3](ClO4)2·H2O (1). The X-ray crystal structure of the hemi acetonitrile solvate [CuL3](ClO4)2·0.5CH3CN has been determined which shows Jahn-Teller distortion in the CuN6 core present in the cation [CuL3]2+. Complex 1 gives an axial EPR spectrum in acetonitrile-toluene glass with g|| = 2.262 (A|| = 169 × 10−4 cm−1) and g⊥ = 2.069. The Cu(II/I) potential in 1 in CH2Cl2 at a glassy carbon electrode is 0.32 V versus NHE. This potential does not change with the addition of extra L in the medium implicating generation of a six-coordinate copper(I) species [CuL3]+ in solution. B3LYP/LanL2DZ calculations show that the six Cu-N bond distances in [CuL3]+ are 2.33, 2.25, 2.32, 2.25, 2.28 and 2.25 Å while the ideal Cu(I)-N bond length in a symmetric Cu(I)N6 moiety is estimated as 2.25 Å. Reaction of L with Cu(CH3CN)4ClO4 in dehydrated methanol at room temperature even in 4:1 M proportion yields [CuL2]ClO4 (2). Its 1H NMR spectrum indicates that the metal in [CuL2]+ is tetrahedral. The Cu(II/I) potential in 2 is found to be 0.68 V versus NHE in CH2Cl2 at a glassy carbon electrode. In presence of excess L, 2 yields the cyclic voltammogram of 1. From 1H NMR titration, the free energy of binding of L to [CuL2]+ to produce [CuL3]+ in CD2Cl2 at 298 K is estimated as −11.7 (±0.2) kJ mol−1. 相似文献
2.
G. Attilio Ardizzoia Stefano Brenna Fulvio Castelli Simona Galli 《Inorganica chimica acta》2009,362(10):3507-3512
Different imine-type ligands, prepared by the condensation of anilines or of α-methylbenzylamine with 2-pyridinecarboxaldehyde (pyim1,2) or 2-quinolinecarboxaldehyde (quim1,2) were prepared. These species act as N,N′-bidentate, chelating ligands upon coordination to Cu(I): treatment of [Cu(PPh3)3Cl] with an equimolar amount of the ligands resulted in the displacement of two molecules of PPh3, giving rise to the formation of [Cu(pyim1,2)(PPh3)Cl] (1-2) and [Cu(quim1,2)(PPh3)Cl] (3-4), respectively. The copper derivatives 1-4 proved to be highly active catalysts in olefin cyclopropanation in the presence of ethyl diazoacetate, even using deactivated olefins (namely, 2-cyclohexen-1-one) as substrate. The X-ray structure of complex 2, [Cu(pyim2)(PPh3)Cl], is also reported. 相似文献
3.
《Inorganica chimica acta》1986,115(1):55-63
A series of silver and copper coordination complexes has been studied using secondary ion mass spectrometry (SIMS). Results are presented for the monomeric silver(I) complexes [Ag(CNR)4]X, where R = cyclohexyl for X ClO4−, and R = methyl or t-butyl for X PF6−. Likewise, Cu(I) complexes [Cu(CNR)4]PF6, where R =methyl, t-butyl, or cyclohexyl, were examined. The presence of AgL2+ (L represents the intact RNC ligand) and the absence of AgL3+ and AgL4+ species attests to the gas phase stability of two-coordinate silver(I). Similar results to these were obtained for the Cu(I) complexes, with the exception of [Cu(CNCH3)4]PF6 whose spectrum contains CuL4+, CuL3+, CuL2+, CuL+, and Cu+ ions. The latter result reflects the enhanced stability of the tetrahedral Cu(I) geometry compared to Ag(I) in the gas phase. Cross labeling experiments and isotopic labeling studies have provided insights into fragmentation mechanisms. Ligand exchange occurs when mixtures are examined. These exchange reactions provide evidence for extensive molecular mixing which can accompany SIMS even under low primary ion dose conditions. Cluster ion formation as well as the observation of α-cleavage of the NC bonds of RNC ligands have been observed and these results are discussed. Granulated graphite and ammonium chloride were employed to study matrix effects. Granulated graphite enhanced NC cleavage for the silver complexes but had little effect on the relative abundance of silver cluster ions. On the other hand, copper cluster ions were more sensitive to matrix effects. 相似文献
4.
A series of monomeric tetrahedral complexes of stoichiometry, [MX(HL)(Ph3P)2] (In case of M = Cu, H1L, X = I, 1; Br, 2; Cl, 3; H3L, X = I, 4; Br, 5; Cl, 6; H4L, X = I, 7; Br, 8; Cl, 9 and in case of M = Ag, H1L, X = Cl, 13; Br, 14; H2L, X = Cl, 15, Br 16; H3L, X = Cl, 17, Br, 18) were synthesized by the reaction of copper (I) or silver (I) halides with indole-3-thiosemicarbazone (H1L) or 5-methoxy indole-3-thiosemicarbazone (H2L) or 5-methoxy indole-N1-methyl-3-thiosemicarbazone (H3L), whereas dimers of stoichiometry, [Cu2(μ-X)2(η1-S-H2L)2(Ph3P)2] (X = I, 10; Br, 11; Cl, 12) were obtained by the reaction of copper (I) halides with indole-N1-methyl-3-thiosemicarbazone (HIntsc-N1-Me, H2L). The synthesized complexes were characterized using NMR (1H and 13C) and single crystal X-ray diffraction (H2L, 3, 7, 8, 10, 11 and 13) as well as elemental analysis. Anti- M. tuberculosis activity of ligands (H1L-H4L) and their metal complexes (1–18) were evaluated against M. tuberculosis H37RV strain ATCC 27294. It has been observed that there is unusual enhancement in anti TB activity of these ligands on complexation with copper (I) and silver (I). Molecular modelling studies in the active binding site are also giving complementary theoretical support for the experimental biological data acquired. 相似文献
5.
《Inorganica chimica acta》1988,145(1):105-109
Copper(I) chloride and bromide reacted with an equimolar amount of ferrocenyldiphenylphosphine (PFcPh2) in refluxing benzene, affording the new tetrameric complexes [CuX(PFcPh2)]4 (1, X= Cl; 2, X = Br) as yellow microcrystals. Their bipyridyl (bpy) derivatives [CuX(bpy)(PFcPh2)] (3, X=Cl; 4, X=Br) were prepared also. When copper(I) chloride was allowed to react with abundant PFcPh2, only the mononuclear complex [CuCl(PFcPh2)2] (5) was isolated. THF solutions of the copper(I) complexes and 2,5-norbornadiene (Nbd) were irradiated at 366 nm, and the valence isomerization of Nbd to quadricyclene (Q) was observed. Quantum yields with 1 and 2 were about 0.011 and 0.008, respectively, and those with other complexes were very small. 31P NMR studies were performed for the complexes in the presence of Nbd or norbornene, and the key photoactive species in the isomerization with 1 and 2 were determined to be their ground state copper-Nbd adducts, i.e. ‘CuX(PFcPh2)(Nbd)’. Photoexcitation of the adducts was assumed to give rise to the valence isomerization and to release Q. 相似文献
6.
A molecular rectangle [Cu{CuL1(NO3)}(H2O)(NO3)]2 (1) and two infinite molecular rectangle strands {[Cu{CuL1(NO3)}2] · 2H2O}∞ (2) and [Cu{CuL2(ClO4)}2]∞ (3) were prepared by reaction of “naked” Cu(II) ions with macrocyclic complex ligands CuL1 for 1 and 2 and CuL2 for 3 in metal-to-ligand molar ratios of 1:1, 1:2 and 1:2, respectively. L1 and L2 denote the dianions of diethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate and diethyl 5,6,7,8,15,16-hexahydro-15-methyl-6,7-dioxodibenzo[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate, respectively. The structures of 1-3 were determined by X-ray single-crystal analyses. CuL1 in 1 and 2 and CuL2 in 3 act as angular linkers with a monodentate coordination top and a bidentate one between two Cu(II) nodes to enclose the molecular rectangle of 1 and the rectangular subunits of 2 and 3. The angular shape, the monodentate top plus bidentate top coordination mode and the self-complementarity for π?π interactions of the macrocyclic complex linkers, the ratio between the reactants and the octahedral coordination geometry of the naked Cu(II) ions jointly determined the interesting structures of metallocyclophane 1 and 1D double chain coordination polymers 2 and 3. The cavities of the rectangular molecules of 1 are arranged into infinite strands so that parallel channels occur in the crystal. The molecules of 2 and 3 all pack parallel in the crystals. 相似文献
7.
Spinach plastocyanin was converted into the apoprotein. CuSO4 and oxidized Cu(II)- thionein reacted with the apoprotein to Cu(II) plastocyanin. Cu(I) transfer from Cu(I)0-thionein was only 15%. The structural analogue of the copper thiolate chromophore [Cu(I)(thiourea)3]Cl as well as [Cu(CH3CN)4]ClO4 successfully formed the Cu(I)- holoprotein. Characteristic circular dichroism bands at θ284 (?5300 deg·cm2·dmol?1 and θ310 (+3300 deg·cm2·dmol?1) were seen. Upon oxidation with ferricyanide and dialysis against phosphate buffer the correct Cu(II) binding into the active centre of Cu(II) plastocyanin was confirmed by EPR-measurements. The use of [Cu(I)(thiourea)3] Cl as a convenient Cu(I) source for reconstitution studies on copper proteins is highly recommended. 相似文献
8.
Cyclic voltammetry in acetonitrile has been used to study the redox properties of the compound [Cu-(BBDH)Cl] Cl under various conditions. The nature of the species in solution was studied with the aid of ligand-field spectra and ESR spectra. It appears that in CH3CN solution two Cu(II) species are predominating, viz. [Cu(BBDH)(CH3CN)x]2+ and Cu(BBDH)-Cl+. Minor species are dimeric in nature, such as [(BBDH)CuCl2Cu(BBDH)]2+, as easily seen from ESR. The relative amount of the two major species was varied using added LiCl, allowing us to determine the nature of both species. The redox potential of the species [Cu(BBDH)Cl]+ appeared to be 0.62 V (against a normal hydrogen electrode), which is very high for a Cu(II) compound and in the same area as found for the blue copper proteins. Re-oxidation of Cu(BBDH)+ in the presence of LiCl shows that C slowly recoordinates after reoxidation. 相似文献
9.
Juan-Juan Hou 《Inorganica chimica acta》2007,360(1):14-20
Hydrothermal reaction of copper(II) chloride with 2-hydroxypyrimidine generated double salt of [Cu2Cl(μ4-pymo)] (1) (Hpymo = hydroxylpyrimidine) while hydrothermal treatment of CuCl2, NaN3 and acetonitrile resulted in double salt of [Cu2(mtta)Cl] (2) (Hmtta = 5-methyltetrazole) in which in situ [2 + 3] cycloaddition reactions of acetonitrile with azide formed mtta ligand. X-ray single crystal structural analyses revealed that 1 shows a two-dimensional layer formed by fusion of one-dimensional structural motifs. The two-dimensional layers in 1 are held together by C-H?Cl hydrogen bonds to form three-dimensional supramolecular array. Compound 2 has a three-dimensional framework constructed from ribbons and [Cu8Cl4]4+ units. Uncommon coordination modes of μ4-1,2κO:3κN:4κN′ pymo and μ4-Cl (Cl at the apex of a Cu4Cl square pyramid) in 1 and μ4-η1:η1:η1:η1 mtta in 2 were also observed. The short Cu(I)?Cu(I) distances were found in 1 and 2, indicating the existence of Cu(I)?Cu(I) interactions. 相似文献
10.
Some copper(I) complexes of the type [Cu(L)(dppe)]X (1-4) [where L = (3-trifluoromethylphenyl)pyridine-2-ylmethylene-amine; dppe = 1,2-bis(diphenylphosphino)ethane; X = Cl−, CN−, ClO4− and BF4−] have been synthesized by the condensation of 3-aminobenzotrifluoride with 2-pyridinecarboxaldehyde followed by the reaction with CuCl, CuCN, [Cu(MeCN)4]ClO4 and [Cu(MeCN)4]BF4 in presence of dppe. The complexes 1-4 were then characterized on the basis of elemental analysis, IR, UV-Vis and 1H NMR spectral studies. The representative complex of the series 4 has been characterized by single crystal X-ray diffraction which reveal that in complex the central copper(I) ion assumes the irregular pseudo-tetrahedral geometry. The catalytic activity of the complexes was tested and it was found that all the complexes worked as effective catalyst in the amination of aryl halide. 相似文献
11.
New copper(II) complexes [CuL2]2+ (L2=7,7,9-trimethyl-1,3,6,10,13-pentaazabicyclo[11,2,11.13]hexadec-9-ene) and [Cu2(L3)(H2O)2]4+ have been prepared by the reaction of [CuL1]2+ (L1=5,5,7-trimethyl-1,4,8,11,14-pentaazatetradce-7-ene) and formaldehyde. The mononuclear complex [CuL2]2+ has a square-planar coordination geometry with a 5-6-5-6 chelate ring sequence and is relatively stable even in low pH at room temperature. The dinuclear complex [Cu2(L3)(H2O)2]4+ consists of two unsaturated 15-membered pentaaza macrocyclic units (7,7,9-trimethyl-1,3,6,10,13-pentaazacyclopentadec-9-ene) that are linked together by a methylene group in a tilted face-to-face arrangement [Cu?Cu distance: 7.413(2) Å ]. Each macrocyclic unit of [Cu2(L3)(H2O)2]4+ contains one four-membered chelate ring and has a severely distorted octahedral coordination polyhedron. The dinuclear complex is quite stable in aqueous solutions containing an excess of formaldehyde or in dry acetonitrile but is decomposed to [CuL1]2+ and [CuL2]2+ in pure water. 相似文献
12.
Mark B. Bushuev Viktor P. Krivopalov Dmitrii Yu. Naumov Katerina A. Vinogradova Lilia A. Sheludyakova Stanislav V. Larionov 《Inorganica chimica acta》2010,363(7):1547-13900
A new bidentate chelating pyrazolylpyrimidine ligand bearing a strong electron-donating substituent, i.e. 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine (L) (Scheme 1), has been synthesized and used to obtain the copper(II) complexes by reaction with CuCl2. The molar ratio Cu:L = 1:2 leads to isolation of a complex having CuL2Cl2 empirical formula, while the molar ratio Cu:L = 1:1 gives a complex with CuLCl2 empirical formula. The crystal structure of L as well as the structures of both complexes were studied by single crystal X-ray diffraction. The crystal structure of CuL2Cl2 compound is formed by trans-[CuL2Cl2] mononuclear molecules. Surprisingly, in contrast to the previous compound having molecular structure, the crystal structure of CuLCl2 consists of mononuclear [CuL2Cl]+ complex cations and dinuclear [Cu2Cl6]2− anions. Thus, formula of CuLCl2 complex can be represented as [CuL2Cl]2[Cu2Cl6]. In both complexes molecules of L adopt bidentate chelating coordination mode through N2 atom of pyrazole and N3 atom of pyrimidine rings forming five-membered CuN3C metallocycles. Owing to C-H···N interactions and π-π-stacking L molecules form 2D network. In the structure of trans-[CuL2Cl2] there exist double lone pair(N(piperidine))-π(pyrimidine) interactions and C-H···Cl contacts resulting in the formation of 1D chains. Layered 2D structure of [CuL2Cl]2[Cu2Cl6] results from C-H···Cl, C-H···π and double lone pair(Cl([CuL2Cl]+ complex cation)-π(pyrimidine) interactions. 相似文献
13.
Petra Bombicz Ilpo Mutikainen Tuula Leskelä Lauri Niinistö 《Inorganica chimica acta》2004,357(2):513-525
Complex formation of thiourea with copper takes place as an intermediate step in the preparation of copper sulfide thin films by spray pyrolysis starting from aqueous solutions of copper(II) chloride and thiourea. The stoichiometry of the complex and that of the resulting thin film primarily depends on the molecular ratio of the starting materials. For comparison, the structures of all copper(I) thiourea complexes found in the Cambridge Structural Database are classified in this paper. In addition, syntheses, structural (single crystal XRD also at low temperature 193 K) and spectroscopic studies (FTIR and Raman) of six copper-thiourea complexes are now reported. The copper to thiourea stoichiometric ratio is 1:3 in four of these complexes, but their structures are basically different as dimerization or polymer formation takes place depending on whether the water of crystallisation is present or absent. The structure of bis(μ-thiourea)tetrakis(thiourea)dicopper(I) dichloride dihydrate, [Cu2(tu)6]Cl2 · 2H2O (1) was determined at room and also at low temperature. Bis(μ-thiourea)tetrakis(thiourea)dicopper(I) dibromide dihydrate, [Cu2(tu)6]Br2 · 2H2O (2) is isomorphous with 1, like the anhydrous compounds chlorotris(thiourea)copper(I), [Cu(tu)3]Cl (3) and bromotris(thiourea)copper(I), [Cu(tu)3]Br (4) are isomorphous. In the third isomorphous pair of complexes the copper to thiourea stoichiometric ratio is 1:1, viz. chloro(thiourea)copper(I) hemihydrate, [Cu(tu)]Cl · 0.5H2O (5) and bromo(thiourea)copper(I) hemihydrate, [Cu(tu)]Br · 0.5H2O (6). During the preparation of chloro(thiourea)copper(I) hemihydrate (5) a reaction by product α,α′-dithiobisformamidinium dichloride, [SC(NH2)2]2Cl2 (7) was identified and structurally characterized which made it possible to suggest a reaction path leading to complex formation. 相似文献
14.
The reaction of the tripod ligand hydrotris(2-mercapto-1-imidazolyl)borate Tmxylyl with zinc(II) perchlorate in methanol afforded the mononuclear complex of the type [Tmxylyl-Zn(mimxylyl)]ClO4 (1). Whereas under the same conditions, the reaction with copper(II) perchlorate gives rise to the simultaneous formation of the dinuclear copper(I) complex [TmxylylCu]2 (2). The chemical formulae of the complexes have been characterized by elemental chemical analysis, IR-NMR spectroscopies, and single crystal X-ray methods. In complex 1, the zinc(II) atom displays a distorted tetrahedral environment. While in complex 2, the Tmxylyl ligand bridges the two copper(I) atoms in an asymmetric manner with trigonal geometry. The inverted conformation of the ligand Tmxylyl at the boron center, allows the B-H units to be directed towards the copper centers. The greater reactivity of the borohydride groups towards metal centers enhances the reduction of Cu(II) to Cu(I). The obtained kinetic results for the methylation reactions of 1 and 2 indicate that these bound thione complexes are less suitable to electrophilic attack than the thiolate ligand. 相似文献
15.
Juan Guerrero Luis Cortez Liliana Farías Claudio Pettinari Francesco Caruso 《Inorganica chimica acta》2010,363(14):3809-3816
A series of [Cu(I)(2,2′-biquinoline)(L)](ClO4) complexes (L = bis(diphenylphosphino)methane (bppm), 1,2-bis(diphenylphosphino)ethane (bppe), 1,4-bis(diphenylphosphino)butane (bppb)) have been synthesized and characterized by elemental analysis, conductivity, ESI-mass, NMR and UV-Vis spectroscopies, cyclic voltammetry, X-ray diffraction ([Cu(I)(2,2′-biquinoline)(bppe)](ClO4)) and DFT calculations. These compounds are monometallic species in a distorted tetrahedral arrangement, in contrast with related compounds found as dinuclear according to diffraction studies. The spectroscopic properties are not directly correlated with the length of alkyl chain bridge between the bis-diphenylphosphine groups. In this way, the chemical shift of some 2,2′-biquinoline protons and the metal to ligand charge transfer (Cu to 2,2′-biquinoline) follows the order [Cu(2,2′-biquinoline)(bppm)](ClO4), [Cu(2,2′-biquinoline)(bppb)](ClO4), [Cu(2,2′-biquinoline)(bppe)](ClO4). The same dependence is followed by the potentials to Cu(II)/Cu(I) couple. These results are discussed in terms of inter-phosphorus alkane chain length and tetrahedral distortions on copper. 相似文献
16.
Kiyoshi Fujisawa Hiroaki Iwamoto Kengo Tobita Yoshitaro Miyashita Ken-ichi Okamoto 《Inorganica chimica acta》2009,362(12):4500-4509
Copper(II) coordination complexes of the neutral ligand, tris(3-tert-butyl-5-methyl-1-pyrazolyl)methane (L2′), i.e. the copper(II) nitrato complexes [Cu(L2′)(NO3)][Cu(NO3)4]1/2 (1) and [Cu(L2′)(NO3)](ClO4) (2) and the copper(II) chloro complex [Cu(L2′)(Cl)](ClO4) (3), and its anionic borate analogue, hydrotris(3-tert-butyl-5-methyl-1-pyrazolyl)borate (L2−), i.e. the copper(II) nitrato complex [Cu(L2)(NO3)] (4) and the copper(II) chloro complex [Cu(L2)(Cl)] (5), were synthesized in order to investigate the influence of ligand framework and charge on their structure and physicochemical properties. While X-ray crystallography did not show any definitive trends in terms of copper(II) atom geometry in four-coordinate copper(II) chloro complexes 3 and 5, different structural trends were observed in five-coordinate copper(II) nitrato complexes 1, 2, and 4. These complexes were also characterized by spectroscopic techniques, namely, UV-Vis, ESR, IR/far-IR, and X-ray absorption spectroscopy. 相似文献
17.
A di-N-functionalized 14-membered tetraaza macrocycle, [H4L3](ClO4)2 (L3 = 1,8-bis(2-carboxyethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane), has been synthesized by acid hydrolysis of 1,8-bis(2-cyanoethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane (L2). The copper(II) complexes [CuL2](ClO4)2 and [Cu(H2L3)](ClO4)2 were prepared and characterized. The complex [Cu(H2L3)]2+ readily reacts with methanol to yield [CuL4]2+ (L4 = 1,8-bis(2-carbomethoxyethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane). The N-CH2CH2COOH groups of [Cu(H2L3)](ClO4)2 are not coordinated to the metal ion in the solid state but are involved in coordination in various non-aqueous solvents or in aqueous solutions of pH ? 1.0. Interestingly, [CuL4](ClO4)2 exists as two stable structural isomers, 1 (the pendant ester groups are not involved in coordination) and 2 (one of the two ester groups is coordinated to the metal ion), in the solid state; the two isomers can be prepared selectively by controlling ionic strength of a methanol solution of the complex. Crystal structures and coordination behaviors of the two isomers are described. The di-N-cyanoethylated macrocyclic complex [CuL2](ClO4)2 is rapidly decomposed in 0.1 M NaOH solution even at room temperature. On the other hand, [Cu(H2L3)](ClO4)2 and [CuL4](ClO4)2 are quite inert against decomposition under similar basic conditions. In acidic or basic aqueous solutions, [CuL4]2+ is hydrolyzed to [Cu(H2L3)]2+ or [CuL3]. 相似文献
18.
Aliakbar Dehno Khalaji Matthias Weil Marzieh Daryanavard 《Inorganica chimica acta》2009,362(13):4837-4842
The reaction of the bidentate Schiff-base ligands (3,4,5-MeO-ba)2en (L1) and (4-Me-ba)2en (L2) with Cu(SCN) in CH3CN yielded two copper(I) coordination polymers [Cu(L1)(SCN)]n (1) and [Cu(L2)(SCN)]n (2), which have been characterized by elemental analyses, IR- and 1H NMR-spectroscopy, and X-ray crystallography. The non-centrosymmetric structures of both Cu(I) complexes consist of an one-dimensional polymeric chain in which copper(I) ions are bridged by two thiocyanate groups bonding in an end-to-end fashion. The Cu(I)?Cu(I) separation is 5.604 Å in 1 and 5.706 Å in 2. 相似文献
19.
G. Attilio Ardizzoia Stefano Brenna Fulvio Castelli Simona Galli Norberto Masciocchi 《Inorganica chimica acta》2010,363(2):324-790
Two new 2,4-dihydro-1H-benzo[d][1,3]oxazines (L1 and L2) were prepared by condensation of 2-quinolinecarboxaldehyde and 2-amino-benzyl alcohols and tested as N,N’-bidentate ligands toward CuCl2. Treatment of the resulting copper(II) derivatives with Et3N promoted an oxidative dehydrogenation yielding the corresponding copper(I) [Cu(L-ox)Cl] complexes, 2, (L-ox = 4H-benzo[d][1,3]oxazine). The [Cu(L2-ox)Cl] species, 2b, was characterized by single crystal X-ray diffraction, showing a trigonal geometry at the metal center and reacted with PPh3 and CO, affording [Cu(L2-ox)(PPh3)Cl], 4b, and [Cu(L2-ox)(CO)Cl], 6b, respectively. The latter species, stable in the solid state, was structurally characterized by diffraction methods and showed tetrahedral coordination of the Cu(I) ion. 相似文献
20.
Razia Sultana Renu Sharma Takashiro Akitsu Yoshikazu Aritake 《Inorganica chimica acta》2010,363(13):3432-3441
Heterocyclic thioamides, namely, imidazolidine-2-thione (imdzSH), 1-methyl-1, 3-imidazoline-2-thione (mimzSH), thiazolidine-2-thione (tzdSH) and 2,4-dithiouracil (dtucH2) with silver(I)/copper(I) salts in presence of triphenyl phosphine (PPh3) have yielded complexes of different nuclearity: mononuclear, [Ag(η1-S-HL)(PPh3)2Cl] (HL = imdzSH 1, mimzSH 2, tzdSH 3), dinuclear, [Ag2(η1-S-tzdSH)2(μ-S-tzdSH)2(PPh3)2](NO3)24, and polynuclear, {Cu(μ-S,S-dtucH2)(PPh3)2X} (X = Cl 5, Br 6, I 7). All complexes have been characterized using analytical data, IR and multinuclear NMR spectroscopy (1H, 13C and 31P) and single crystal X-ray crystallography. The thio-ligands are bonded to the metal centers as neutral sulfur donors. The geometry around each metal center is distorted tetrahedral. Complexes 5-7 represent first examples of polymers of 2,4-dithiouracil in its coordination chemistry with metal salts. The hydrogen bonding interactions lead to the formation of 1D (2, 3, 7) and 2D (1, 4-6) sheet structures. 相似文献