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1.
《Journal of Coordination Chemistry》2012,65(19):3419-3431
A series of Cu(II) carboxylate complexes (carboxylate?=?2-fluorobenzoic acid (2-HFBA) or 4-fluorobenzoic acid (4-HFBA)) containing either one chelating 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, and thermal analyses. In [Cu(bipy)(H2O)(2-FBA)2] (1), [Cu(bipy)(H2O)(4-FBA)2] (3), and [Cu(phen)(H2O)(2-FBA)2] (4), Cu is five-coordinate in a square pyramidal geometry and four-coordinate in [Cu(phen)(2-FBA)2] (2). The four complexes are extended into 1-D chains through hydrogen-bonding and π?···?π interactions in 1 and 4, only hydrogen-bonding in 2, and π?···?π interactions in 3. These contacts lead to aggregation and supramolecular self-assembly. 相似文献
2.
Jesus Sanmartín Manuel R. Bermejo José A. García-Vázquez Jaime Romero Antonio Sousa 《Transition Metal Chemistry》1994,19(2):209-211
Summary The electrochemical oxidation of anodic metals (nickel and cobalt) in MeCN solutions of 2-pyridinone (HOpy) or 2-pyridine
methanethiol-1-oxide (HPMTO) or its dimer, 2,2′-dithiodimethyldipyridine-1,1′-dioxide (DPMTO), gives the simple complexes
[Ni(Opy)2]·2H2O, [Co(Opy)2]·2H2O, [Ni(PMTO)2]·2H2O and [Co(PMTO)2]·3H2O. When 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) was added to the electrolytic phase, only three mixed complexes
were obtained: [Ni(Opy)2bipy]·H2O, [Co·(Opy)2phen]·H2O and [Ni(Opy)2phen]·5H2O. The complexes were characterized by their elemental analyses, i.r. spectra and magnetic properties. 相似文献
3.
Jahan B. Ghasemi Shabnam Hooshmand Saeed Rayati 《Journal of inclusion phenomena and macrocyclic chemistry》2013,76(1-2):47-54
A novel, fast and easy single sample measurement has been developed based upon temperature dependence of equilibrium constant in order to determine the enthalpy and entropy changes of a complexation reaction using spectrophotometric temperature titration. The method can be used in determination of the formation constant and thermodynamic parameters of the solutions that there are difficulties in their titration where volatile compounds are studying. Knowledge of component spectra is not required for the analysis. The formation constants of the interactions of ß-di and tri-brominated meso-tetraphenylporphyrins, and meso-tetrakis(4-methylphenyl) and (4-methoxyphenyl) porphyrins with Me2SnCl2 and Bu2SnCl2, have been determined in range of 0–25 °C utilizing van’t Hoff relation, mass balance and equilibrium constant equations by an iterative least squares method with ΔH 0 as adjustable parameter. The outputs of analysis are the equilibrium constants, ligand and adduct spectral profiles, their concentrations as a function of temperature, the adjusted values of the standard enthalpy ΔH 0, and entropy ΔS 0 changes. The order of formation constants of the resulting 1:1 complexes decreased with increasing number of bromide substituents and increased with adding methyl and methoxy groups, and vary as H2T(4-CH3O)PP > H2T(4-CH3)PP > H2TPP > H2TPPBr2 > H2TPPBr3 and Me2SnCl2 > Bu2SnCl2. 相似文献
4.
Jos Ruiz M. Teresa Martínez Consuelo Vicente Venancio Rodríguez Gregorio Lpez Jos Prez Penny A. Chaloner Peter B. Hitchcock 《无机化学与普通化学杂志》2005,631(11):2227-2231
Mononuclear palladium‐hydroxo complexes of the type [Pd(N–N)(C6F5)(OH)][(N–N) = 2,2′‐bipyridine (bipy), 4,4′‐dimethyl‐2,2′‐bipyridine (Me2bipy), 1,10‐phenantroline (phen) or N,N,N′,N′‐tetramethylethylenediamine (tmeda) react with phenols ArOH in tetrahydrofuran giving the corresponding aryloxo complexes [Pd(N–N)(C6F5)(OAr)]. Elemental analyses and spectroscopic (IR, 1H and 19F) methods have been used to characterize the new complexes. The X‐ray crystal structure of [Pd(tmeda)(C6F5)(OC6H4NO2‐p)] has been determined. In the crystal packing the planes defined by two C6H4 rings show a parallel orientation. There are also intermolecular C–H···F and C‐H···O hydrogen bonds. 相似文献
5.
《Journal of Coordination Chemistry》2012,65(4):638-649
Eight new platinum(II)/palladium(II) complexes with 4-toluenesulfonyl-L-amino acid dianion and diimine/diamine ligands, [Pd(en)(Tsile)]·H2O (1), [Pd(bipy)(Tsile)] (2), [Pd(bipy)(Tsthr)]·0.5H2O (3), [Pd(phen)(Tsile)]·0.5H2O (4), [Pd(phen)(Tsthr)]·H2O (5), [Pd(bqu)(Tsthr)]·1.5H2O (6), [Pt(en)(Tsser)] (7), and [Pt(en)(Tsphe)]·H2O (8), have been synthesized and characterized by elemental analyses, 1H NMR and mass spectrometry. The crystal structure of 7 has been determined by X-ray diffraction. Cytotoxicities were tested by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide and sulforhodamine B assays. The complexes exert cytotoxicity against HL-60, Bel-7402, BGC-823, and KB cell lines with 4 having the best cytotoxicity against HL-60, Bel-7402, and BGC-823 cell lines; the compounds are less cytotoxic than cisplatin. 相似文献
6.
《Journal of Coordination Chemistry》2012,65(2):300-313
Manganese(IV) complexes [MnIV(npah)(H2O)2] (1) and [MnIV(npah)(A)2]?·?nH2O (where A?=?py (2), 2-pic (3), 3-pic (4), 4-pic (5)) and MnIV(npah)(NN)] (NN?=?bpy (6) and phen (7)) have been synthesized from bis(2-hydroxy-1-naphthaldehyde)adipoyldihydrazone in methanol. The composition of the complexes has been established by elemental analyses. Complex 3 has been characterized by mass spectral data also. Structural assessment of the complexes has been based on data from molar conductance, magnetic moment, electronic, electron paramagnetic resonance, and infrared (IR) spectral studies. Molar conductances of the complexes in DMSO suggest non-electrolytes. Magnetic moment and EPR studies suggest +4 oxidation state for manganese in these complexes. Electronic spectral studies suggest six-coordinate octahedral geometry around the metal ions. IR spectra reveal that H4npah coordinates to the metal in enol form. Reaction of the complexes with benzyl alcohol and SO2 has been investigated. Cyclic voltammetric studies of the complexes have also been carried out. 相似文献
7.
Novel Copper(II) Thiodibenzoic Acid Coordination Polymers by in situ Extrusion of Sulfur from 2,2′‐Dithiodibenzoic Acid and the Unique Oxidation of Disulfide to Sulfate
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Salma B. Moosun Lisa H. Blair Simon J. Coles Sabina J. Laulloo Minu G. Bhowon 《无机化学与普通化学杂志》2015,641(5):890-895
Slow diffusion reaction of 2,2′‐dithiodibenzoic acid (dtdb) with CuCl2 in the presence of N‐donor ligands results in the formation of different coordination polymers where both S–S and C–S scission and oxidation of S is observed. X‐ray diffraction analysis of [Cu(tdb)(phen)(H2O)]2 · 2H2O.2DMF] ( 1 ), [Cu(tdb)(py)2(H2O)]2 ( 3 ), and [Cu(tdb)(bipy)(H2O)]2 · 0.5H2O ( 4 ) (tdb = thiodibenzoic acid, phen = phenanthroline, py = pyridine, bipy = 2,2′‐bipyridine) show that the metal ions are coordinated to the carboxylate oxygen atoms of the in situ generated tdb ligand in a monodenate fashion. In [Cu(phen)(SO4)2(H2O)2]n ( 2 ) and [Cu(bipy)(SO4)2(H2O)2]n ( 5 ), the sulfur is oxidized to sulfate ions prior to coordination with the metal. Complex 1 has a dimeric structure with π–π interactions between the phen ligands, whereas 3 and 4 form 1D polymeric chains. 相似文献
8.
《Polyhedron》1986,5(9):1429-1436
A comparative study of the catalyzed decomposition of hydrogen peroxide using the following copper(II) complex salts, Cu(bipy)(S-threo)Cl · 3H2O, Cu(phen)(S-threo)Cl · 2H2O, Cu(bipy)(S-prol)Cl · 2H2O and Cu(phen)(S-prol)Cl · 2H2O has been made. Kinetic parameters were experimentally determined by the polarographic method at 25°C, pH 7.7 and constant ionic strength (μ = 0.1 M NaNO3). The catalytic behavior of the chelate with 2,2′-bipyridine and S-prolinate was also studied at pH 6.5 and 8.5. The reactivity follows the sequence: [Cu(bipy)S-prol] > [Cu(phen)S-prol] > [Cu(bipy)S-threo] > [Cu(phen)S-threo]. Activation energies are very similar to each other. The pH-dependent exchange of the amino acid ligand with hydrogen peroxide seems to be a critical factor in the reaction pathway. Several reaction mechanisms are proposed. 相似文献
9.
E. I. Davydova T. N. Sevast’yanova A. V. Suvorov G. Frenking 《Russian Journal of General Chemistry》2006,76(4):545-553
Structural and thermodynamic characteristics of adducts GeX4 · nL (n = 1, 2; X = F, Cl, Br; L = NH3, py, bipy, phen) have been calculated by the B3LYP density functional theory method. The enthalpies of sublimation of complexes trans-GeX4 · 2py and the adduct GeCl4 · bipy have been estimated for the first time. The rearrangement energies of the donor and acceptor fragments and the Ge-N bond energies for the 1:1 and 1:2 complexes have been calculated. While the rearrangement energy for germanium halides is lower by 19–63 kJ mol?1 than that for silicon halides, the energy of the donor-acceptor bond in the former case is slightly lower. As a result, germanium adducts are slightly more stable than silicon adducts. 相似文献
10.
Several Schiff bases derived from salicylaldehyde and aminopyridines were found to coordinate with Me2SnCl2 in 1:1 or 1:2 (tin:base) molar ratio in diethylether, depending on the nature of the Schiff base used, to form complexes of the general formula Me2SnCl2·L or Me2SnCl2·2L respectively. These Schiff bases coordinate with Ph2SnCl2 in a similar manner, but if the reaction is carried out in chloroform or if the product formed in ether is dissolved in chloroform then colourless to pale yellow crystals precipitated. The latter were analysed and found to be due to the ionic compounds [H2NpyN–H+]2 [Ph2SnCl4]2? which were formed as a result of an unusual cleavage of the C?N bond of the Schiff bases. The Schiff bases, their Me2SnCl2 complexes and the ionic compounds were analyzed physicochemically and spectroscopically. The crystal structures of two of the ionic compounds showed that the cation [H2NpyN–H+] binds with the anion [Ph2SnCl4]2? via hydrogen bonds. The Schiff bases, their Me2SnCl2 complexes and the ionic compounds were screened against the three tumour cell lines, L929, K562 and HeLa, and the results were compared with those of the anticancer drugs, cisplatin, carboplatin and oxaliplatin. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
11.
Synthesis,Structures and DFT Studies of Imido‐bridged and (Bis)ligand‐coordinated Titanium Complexes
Jian Wu Yanmei Chen Zhou Chen Wei Liu Yahong Li Hao Pei Yonglu Liu Qian Gao Wu Li 《无机化学与普通化学杂志》2013,639(10):1876-1883
Syntheses and structures of five imido‐bridged dinuclear titanium complexes and two (bis)ligand‐coordinated mononuclear titanium complexes are reported. Addition of 1 or 2 equiv. of Schiff base ligand (((1H‐pyrrol‐2‐yl)methylene)amino)‐2,3‐dihydro‐1H‐inden‐2‐ol (H2L) to Ti(NMe2)4 resulted in transamination with 4 equiv. of dimethylamides generating a (bis)ligand‐coordinated complex Ti(L)2 ( 1 ). Treatment of Ti(NMe2)4 with 1 equiv. of tBuNH2 followed by addition of 1 equiv. of H2L afforded an imido‐bridged complex [Ti(L)(NtBu)]2 ( 2 ). 1:1:1:1 reaction of Ti(NMe2)4/RNH2/H2L/py(or phen) produced imido‐bridgedcomplexes [Ti(L)(NPh)(py)]2 ( 3 ), [Ti(L)(4‐F‐PhN)(py)]2·Tol ( 4 ·Tol), [Ti(L)(4‐Cl‐PhN)(py)]2·Tol·THF ( 5 ·Tol·THF), [Ti(L)(4‐Br‐PhN)(py)]2·Tol ( 6 ·Tol) and a (bis)ligand‐coordinated complex Ti(L)2·phen ( 7 ) (py = pyridine, phen = 1,10‐phenanthroline). Attempts to prepare the monomeric titianium imido complexes were unsuccessful. DFT studies show that the assumed compound which contains Ti = N species is less stable than imido‐bridged Ti‐N(R)‐Ti complexes, providing the better understanding of the experimental results. 相似文献
12.
Two palladium(II) complexes, [Pd(bipy)(BzPhe‐N,O)] and [Pd(phen)(BzPhe‐N,O)]·4H2O were synthesized by reactions between Pd(bipy)Cl2 and BzPheH2 (N‐benzoyl‐β‐phenylalanine), Pd(phen) Cl2 and BzPheH2 in water at pH‐9, with their structures determined by X‐ray diffraction analysis. The Pd atom is coordinated by two nitrogen atoms of bipy (or phen), the deprotonated amido type nitrogen atom and one of the carboxylic oxygens of BzPhe (BzPhe = N‐benzoyl‐β‐phenylalaninate dianion). In the complex [Pd(phen) (BzFne‐N,O)] · 4H2O, the side chain of phenylalanine is located above and approximately parallels to the coordination plane. Both the aromatic‐aromatic stacking interaction between the phenyl ring of phenylalanine and phen, and the metal ion‐aromatic interaction between the phenyl ring of phenylalanine and Pd(II) were observed. [Pd(bipy)(BzPhe‐N,O)] has the phenylalanyl side chain oriented outwards from the coordination plane, which is mainly due to the interaction between the carbonyl oxygen atom of the amido group and the phenyl ring of phenylalanine. The reason for the different orientation of phenylalanyl side chain in the complexes was suggested. 相似文献
13.
《Journal of Coordination Chemistry》2012,65(7):1239-1251
Monometallic zinc(II) and nickel(II) complexes, [Zn(H2nsh)(H2O)] (1) and [Ni(H2nsh)(H2O)2] (2), have been synthesized in methanol by template method from bis(2-hydroxy-1-naphthaldehyde)succinoyldihydrazone (H4nsh). Reaction of monometallic complexes with alternate metal(II) acetates as a transmetallator in 1 : 3 molar ratio resulted in the formation of heterobimetallic complexes [NiZn(nsh)(A)3] and [ZnNi(nsh)(A′)2] (A = H2O (3), py (4), 2-pic (5), 3-pic (6), 4-pic (7)), (A′ = H2O (8), py (9), 2-pic (10), 3-pic (11), and 4-pic (12)). The complexes have been characterized by elemental analyzes, mass spectra, molar conductance, magnetic moments, electronic, EPR, and IR spectroscopies. All of the complexes are non-electrolytes. Monometallic zinc(II) is diamagnetic while monometallic nickel(II) complex and all heterobimetallic complexes are paramagnetic. The metal centers in heterobimetallic complexes are tethered by dihydrazone and naphthoxo bridging. Zinc(II) is square pyramidal; nickel(II) is six-coordinate distorted octahedral except [ZnNi(nsh)(A)2], in which nickel(II) has square-pyramidal geometry. The displacement of metal center in monometallic complexes by metal ion has been observed in the resulting heterobimetallic complexes. 相似文献
14.
《Journal of Coordination Chemistry》2012,65(17):2703-2714
The ligand N-(2-propionic acid)-salicyloyl hydrazone(H3L, 1) and its new transition metal(II) complexes [NiHL(bipy)H2O] (2), [CdHL(bipy)(H2O)2]2·2H2O (3) and [NiHL(phen)H2O]·H2O (4) (HL is a dianion, bipy?=?2,2′-bipyridine and phen?=?1,10-phenanthroline) were synthesized and characterized on the basis of elemental analyses, IR, 1H NMR, molar conductivity and thermal analysis. Single crystal X-ray diffraction showed that 1 is in keto form and connected by hydrogen bonds to form a two-dimensional supermolecular compound. Complexes 2 and 4 have the same structure with distorted meridional octahedral geometry with 1 as a tridentate ligand with keto-form coordination by azomethine, carboxyl O and acyl O. In 3, ligand 1 bridges two Cd(II) atoms by μ 2-O of carboxyl. H-bonding is an important weak interaction for constructing supermolecular frameworks. There are π–π interactions between bipy or phen rings in 3 or 4, respectively. 相似文献
15.
Lorenzo Pellerito M.Teresa Lo Giudice G.C. Stocco John D. Donaldson Susan M. Grimes Peter J. Smith 《Polyhedron》1985,4(4):747-756
The complexes R2SnCl2·(H2glygly), (H2glygly = glycylglycine) (R = Me, Bun, Octn, Ph) and RSnCl3·(H2glygly) 相似文献
16.
Summary Reactions of 2-mercapto-3-phenyl-4-quinazolinone (LH) with PdCl2 · 2H2O and PtCl4 · 5H2O lead to the formation of [ML2 complexes (M = PdII or PtII). Reactions of PdCl2 · 2H2O with LH in the presence ofN-heterocyclic bases yield compounds of type [PdLClB], (B = py, 3-pic, (o-phen)1/2, and (bipy)1/2) or Pd(LH)Cl(imz). PtCl4] · 5H2O reacts with LH in the presence of variousN-heterocyclic bases to give [PtL2B] compounds (B = py, 3-pic, (o-phen)1/2 or (pyrm)1/2) and [PtL2BCl] (B = imz or pz). These complexes have been characterised on the basis of analytical, i.r. and electronic spectral and magnetic measurement studies, and tentative structures for them are proposed. 相似文献
17.
Diego R. Pérez Susana H. Tarulli Oscar V. Quinzani Dr. Jorge Dristas Ricardo Faccio Leopoldo Suescun Alvaro W. Mombrú 《无机化学与普通化学杂志》2007,633(7):1066-1073
Four new lead(II) thiosaccharinate complexes: [Pb(tsac)2H2O] (1) (tsac: thiosaccharinate anion), [Pb2(tsac)4(py)4] (2) (py: pyridine), [Pb(tsac)(o‐phen)2](tsac)·CH3CN (3) (o‐phen: 1,10‐phenantroline), and [Pb(tsac)2(bipy)] (4) (bipy: 2,2′‐bipyridine) were prepared. The infrared and electronic spectra as well as the thermal analysis of all the compounds were recorded and discussed. The thiosaccharinate anion acts in three different coordination forms, one of then reported for the first time. The crystal structures of complexes 2 and 3 have been determined by single crystal X‐ray diffractometry. In complex 2 , two monomeric moieties are joined together forming a symmetric bis‐μ‐sulphur bridged dimer by interaction of two lead(II) atoms through the exocyclic sulphur atoms of two thiosaccharinate ligands. The seven‐fold coordination sphere of each lead atom is completed by two pyridine nitrogen atoms and by another sulfur and two nitrogen atoms of the thiosaccharinate anions. In complex 3 , the lead(II) atom is coordinated by four nitrogen atoms of two 1,10‐phenantroline molecules and by the sulfur and nitrogen atoms of one thiosaccharinate ion. The second anion has an electrostatic interaction with the nucleus. 相似文献
18.
Reactions of aquapentachloroplatinic acid, (H3O)[PtCl5(H2O)]·2(18C6)·6H2O ( 1 ) (18C6 = 18‐crown‐6), and H2[PtCl6]·6H2O ( 2 ) with heterocyclic N, N donors (2, 2′‐bipyridine, bpy; 4, 4′‐di‐tert‐butyl‐2, 2′‐bipyridine, tBu2bpy; 1, 10‐phenanthroline, phen; 4, 7‐diphenyl‐1, 10‐phenanthroline, Ph2phen; 2, 2′‐bipyrimidine, bpym) afforded with ligand substitution platinum(IV) complexes [PtCl4(N∩N)] (N∩N = bpy, 3a ; tBu2bpy, 3b ; Ph2phen, 5 ; bpym, 7 ) and/or with protonation of N, N donor yielding (R2phenH)2[PtCl6] (R = H, 4a ; Ph, 4b ) and (bpymH)+ ( 8 ). With UV irradiation Ph2phen and bpym reacted with reduction yielding platinum(II) complexes [PtCl2(N∩N)] (N∩N = Ph2phen, 6 ; bpym, 9 ). Identities of all complexes were established by microanalysis as well as by NMR (1H, 13C, 195Pt) and IR spectroscopic investigations. Molecular structures of [PtCl4(bpym)]·MeOH ( 7 ) and [PtCl2(Ph2phen)] ( 6 ) were determined by X‐ray diffraction analyses. Differences in reactivity of bpy/bpym and phen ligands are discussed in terms of calculated structures of complexes [PtCl5(N∩N)]— with monodentately bound N, N ligands (N∩N = bpy, 10a ; phen, 10b ; bpym, 10c ). 相似文献
19.
Substitution reactions take place following the photonic excitation of aqueous K4M(CN)8 (where M = Mo or W) in the presence of 1,10-phenanthroline and 2,2bipyridyl. Changes in absorbance with time show that the overall reaction is dependent on photochemical activation of potassium octacyanomolybdate(IV) and -tungstate(IV). The species [K2Mo(CN)4(OH)2(phen)], [K2W(CN)4(OH)2(phen)], [K2Mo(CN)4(OH)2(bipy)] and [K2W(CN)4(OH)2(bipy)] exist in solution. The final photosubstitution products [Mo(OH)3(CN)(phen)2] · 2H2O], [Mo(OH)3(CN)(bipy)2] · 3H2O, [W(OH)3(CN)(phen)2] · 2H2O and [W(OH)3(CN)(bipy)2] · H2O have been isolated in the solid state. Their IR spectra have been discussed. The quantum yield of the photosubstitution reactions has been determined and its variation with change of concentration of the complex as well as the H+ ion concentration has been studied. 相似文献
20.
J. A. Castro J. E. Vilasanchez J. Romero J. A. Garcia-Vazquez M. L. Duran A. Sousa E. E. Castellano J. Zukerman-Schpector 《无机化学与普通化学杂志》1992,612(6):83-88
The electrochemical oxidation of anodic nickel in acetonitrile solution containing both (a) a Schiff base HL derived from H-pyrrole-2-carbaldehyde and a substituted aniline, and (b) a nitrogen ligand (1, 10-phenanthroline (phen), 2,2′-bipyridine (bipy) or pyridine (py)) yielded the mixed complexes NiL2 · phen, NiL2 · bipy and NiL2 · (py)2. The crystal structure of 2,2′-bipyridine bis{2-[(phenyl)iminomethyl]pyrrolato}nickel(II) was determined by X ray diffraction. Crystals are triclinic space group P1 , with four molecules in the unit cell of dimensions a = 12.316(1), b = 13.169(4), c = 17.251(3) Å, α = 82.67(3)°, β = 83.66(1)° and γ = 87.34(2)°, and consist of monomeric molecules in which the central NiN6 unit has a distorted octahedral geometry. 相似文献