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1.

The complexes [N2(L2)2(H2O)4]Cl4(1) and [Ni(L2)](ClO4)2 [sdot]2H2O (2) (L = 1,3,10,12,16,19-hexaazatetracyclo [17,3,1,1 12.16,04.9]tetracosane) have been synthesized and structurally characterized by X-ray crystallography, spectroscopic and cyclic voltammetry. The crystal structure of 1 has a distorted octahedral geometry with two secondary and two tertiary amines of the macrocycle and two water molecules. In 2, the coordination geometry around the nickel atom is square-planar with four nitrogen atoms of the macrocycle. The equilibrium [Ni(L2)]2+ + 2H2O &rlhar2; [Ni(L2)(H2O)2]2+ has been studied in aqueous solution over a temperature range, yielding Δ H° = -19.0 ± 0.2 kJ mol-1 and Δ S° = - 56.0 ± 0.4 JK-1 mol-1. Cyclic voltammetry of the complexes give two one-electron waves corresponding to Ni(II)/Ni(III) and Ni(II)/Ni(I) processes. The electronic spectra and redox potentials of the complexes are influenced significantly by the geometry.  相似文献   

2.

The novel transition metal saccharinato complexes of N-(2-hydroxyethyl)-ethylendiamine (HydEt-en) have been synthesized and characterized by elemental analyses, magnetic moments, UV-Vis and IR spectra. Coordination behaviour of HydEt-en has been studied. The Mn(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) form mononuclear complexes, while the Fe(II) and Co(II) complexes are dimeric. The crystal structures of the [Cu(sac)2(HydEt-en)2] and [Cd(sac)2(HydEt-en)2] complexes, where sac is the deprotonated form of saccharin, were determined by x-ray diffraction. The metal ions are octahedrally coordinated by these ligands. The amine ligand acts as a bidentate N-donor ligand and its ethanol group is not involved in coordination. The sac ions coordinate through the deprotonated N as a monodentate ligand. The NH and OH groups of the amine ligand are involved in intra- and intermolecular hydrogen bonding with the carbonyl and sulphonyl oxygens of the sac ions to form a three-dimensional infinite network.  相似文献   

3.
设计合成了2个结构新颖的半夹心单核聚吡唑硼酸盐羧酸配合物Tp*Co(Hglu)(CH3OH)(1)和Tp*Co(Hsub)(H2O)(2)[Tp*=三聚(3,5-二甲基吡唑)硼酸根, H2glu=戊二酸, H2sub=辛二酸], 并通过元素分析、 红外光谱、 紫外-可见光谱和X射线单晶结构分析对标题配合物进行了表征. 结构分析表明, 在配合物1和2中, 配体Tp*都是三齿配位, 配位模式相同; 戊二酸和辛二酸都以μ111的端基配位模式与金属相连. 此外, 还对配合物的热稳定性进行了详细分析, 并初步探讨了配合物催化氧化环己烷的催化活性.  相似文献   

4.

The synthesis of neutral and cationic palladium complexes containing the tridentate monoanionic ligand [2-(2-Ph2PC6H4-CH=N)C6H4O]? is described. Deprotonation of the Schiff base formed by condensation of 2-(diphenylphosphino)benzaldehyde with 2-aminophenol in the presence of the appropriate palladium precursor ([Pd(AcO)2] or [PdCl2(PhCN)2]) form the corresponding neutral complexes [Pd{2-(2-Ph2PC6H4-CH=N)C6H4O}(AcO)] (1) or [Pd{2-(2-Ph2PC6H4-CH=N)C6H4O}(Cl)] (2) in good yield. The first reacts smoothly with thiols and activated phenols to give complexes of general formula [Pd{2-(2-Ph2PC6H4-CH=N)C6H4O}(X)] (X = OC6F5 (3), SEt (4), StBu (5), SC6H5 (6), SC6H4-4Me (7), SC6H4-4NO2 (8)). When the chloro complex is treated with silver perchlorate and tertiary phosphines (L) the cationic derivatives [Pd{2-(2-Ph2PC6H4-CH=N)C6H4O}(L)][ClO4] (L = PPh3 (9), PMePh2 (10), PMe2Ph (11), PEt3 (12)) were obtained. The new complexes were characterized by partial elemental analyses and spectroscopic methods (IR, 1H, 19F and 31P NMR).  相似文献   

5.

The first 2-pyridylethanol (pyet) complexes of manganese(II), iron(II), cobalt(II), nickel(II), copper(II) and zinc(II) saccharinates, were synthesized and characterized by elemental analyses, magnetic measurements, UV-Vis, and IR spectroscopic techniques. Crystal and molecular structures of the iron(II) and copper(II) complexes were determined by single crystal X-ray diffractometry. The experimental data showed that all the complexes are mononuclear with a general formula [M(H2O)2(pyet)2](sac)2, where sac is the saccharinate anion. All the metal ions are octahedrally coordinated by two aqua and two pyet ligands. The pyet ligand acts as a bidentate ligand through its amine nitrogen and hydroxyl oxygen atoms forming a six-membered chelate ring, while the sac ions remain outside the coordination sphere. All the complexes are isomorphous with a monoclinic space group P21/n and Z = 2.  相似文献   

6.
Two trinuclear CoII and ZnII complexes, [(CoL)2(OAc)2Co] and [(ZnL)2(OAc)2Zn], with an asymmetric Salen‐type bisoxime ligand [H2L = 4‐(N,N‐diethylamine)‐2,2′‐[ethylenediyldioxybis(nitrilomethylidyne)]diphenol] were synthesized and characterized by elemental analyses, IR, UV/Vis, and fluorescent spectroscopy. The crystal structures of the CoII and ZnII complexes were determined by single‐crystal X‐ray diffraction methods. The CoII atom is pentacoodinated by N2O2 donor atoms from the (L)2– unit and one oxygen atom from the coordinated acetate ion, resulting in a trigonal bipyramid arrangement. With the help of intermolecular hydrogen bonding C–H ··· O and C–H ··· π interactions, a self‐assembled continual zigzag chain‐like supramolecular structure is formed. The ZnII atom is pentacoodinated by N2O2 donor atoms from the (L)2– unit and one oxygen atom from the coordinated acetate ion, resulting in an almost regular trigonal bipyramid arrangement. A self‐assembled continual 1D supramolecular chain‐like structure is formed by intermolecular hydrogen bonding C–H ··· O and C–H ··· π interactions. Additionally, the photophysical properties of the CoII and ZnII complexes were discussed.  相似文献   

7.
Three complexes with the ditopic ligand 4′‐[4‐(quinolin‐8‐yloxymethyl)phenyl]‐2,2′:6′,2′′‐terpyridine (abbreviated as L ), [Ni(L)2](CH3COO)2 ( 1 ), [Cd(L)2](ClO4)2 ( 2 ), and [Cu2(L)2](ClO4)4 · 4DMF ( 3 ), were synthesized and characterized by elemental analysis, IR spectroscopy, and structurally analyzed by X‐ray single‐crystal diffraction. Interestingly, in complexes 1 and 2 , two ligands adopt a tridentate chelating pattern where the oxaquinoline group is non‐coordinated and coordinate with one MII ion (M = Ni for 1 , M = Cd for 2 ) to form a mononuclear unit. In complex 3 , two ligands bridge two CuII ions by pyridyl N atoms, ethereal O atoms, and quinolyl N atoms in a head‐to‐tail mode to generate a dinuclear [Cu2L2] unit. Moreover, extended 1D and 2D supramolecular architectures are further constructed in 1 – 3 by multiple secondary interactions such as aromatic stacking and hydrogen bonding. Notably, the structural diversity of complexes 1 – 3 can be properly assigned to the central metal ions that have distinct coordination preferences. In addition, luminescent properties of the ligand and complex 2 were also investigated.  相似文献   

8.
Three new coordination polymers, namely, [CuL0.5] ( 1 ), [Co(H2L)(H2O)2][H2O] ( 2 ), and [(CdCl)0.5Cd0.25(H2L)0.5] ( 3 ) were synthesized under hydrothermal conditions from the corresponding CuII, CoII, and CdII salts with a multidentate ligand of 2,2′,2′′,2′′′‐[2,3,5,6‐tetramethyl‐1,4‐phenylenebis(methylenenitrilo)]tetraacetic acid (H4L). The complexes were characterized by single‐crystal X‐ray diffraction, IR, thermogravimetric, and elemental analyses. Complex 1 crystallizes in the orthorhombic space group Pbca and has a three‐dimensional architecture with infinite two‐dimensional networks linked together by weak Cu–O interactions. Complex 2 crystallizes in the monoclinic space group P2(1) and displays a 2D network. Complex 3 crystallizes in the tetragonal space group P4(2)/ncm and exhibits an infinite 3D architecture that has unusual [Cd2(CO2)4Cl2] dinuclear paddle‐wheel units and [Cd(CO2)4] dodecahedron units. The results showed that the coordination arrangement of central metal atoms and the conformation and coordination mode of organic ligands play an important role in determining the structure of the complexes. The luminescence property of complex 3 was studied in the solid state at room temperature.  相似文献   

9.

The complexes [Co(eee)(bipy)]Cl3 and [Co(eee)(phen)]Cl3 (eee, 1,8-diamino-3,6-dithiaoctane) were synthesized and characterized by two-dimensional NMR spectroscopy. The presence of the bidentate aromatic ligands 2,2-bipyridine and 1,10-phenanthroline caused the 1H resonances to be spread into a wider spectral width than previously observed for [Co(eee)(NO2)2]Cl and [Co(eee)Cl2]Cl. Separate multiplets were observed for the four protons in the terminal ethylene linkage. It was possible to positively assign each multiplet and to determine the relative spatial orientations of the corresponding protons.  相似文献   

10.

Four manganese(III) complexes, [Mn(salMeDPT)(O 2 CMe)] 1 , [Mn(salMeDPT)Cl]·MeCN 2 , [Mn(salEDPA)] Cl 3 and [Mn(salEDPA)](MeCO 2 ) 4 have been prepared, where the di-Schiff-base salMeDPT and salEDPA were from the (2 + 1) condensation of salicylaldehyde with 4-methyl-4-azaheptane-1,7-diamine and with 4,7-diazadecane-1,10-diamine, respectively. The four complexes have been characterized by elemental analyses and cyclic voltammetry, while complexes 1 - 3 have also been characterized by single-crystal x-ray diffraction, which reveals all the Mn(III) atoms in these complexes adopt slightly compressed octahedra with the Mn-O and Mn-N bond lengths in ranges 1.882(3)-1.890(3) and 2.021(4)-0.546(4) Å, respectively. The results of activity assay indicate that complexes 1 - 4 have moderate superoxide dismutase activities.  相似文献   

11.

Oxovanadium(IV), isothiocyanatomanganese(III), cyanocobalt(III) and cobalt(II) complexes of tetraaza[14]annulene appended with two crown ethers at 2,3- and 11,12-positions have been prepared. Cation complexation behavior of these cavity-bearing tetraaza[14]annulene complexes has been investigated by optical absorption methods. The cation K + , which necessitates two crown ether cavities for complexation, induces dimerization of the tetraaza[14]annulene complexes, whereas the Na + does not. Formation of the sandwich complexes due to dimerization is hindered by the steric interactions involving the axial ligand as judged by the blue shift of the intense band around 385-425 nm. Judging from its ESR spectrum, the cobalt(II) complex becomes a monomeric dioxygen complex of a 1 : 1 molar ratio in the presence of O 2 and pyridine at 77 K.  相似文献   

12.
Three coordination complexes, namely, [Zn(btbp)(3‐npa)]n ( 1 ), [Co(btbh)(3‐npa)]n ( 2 ), and {[Co(btbb)(5‐nipa)(H2O)] · H2O}n ( 3 ) (btbp = 1,3‐bis(thiabendazole)propane, btbh = 1,6‐bis(thiabendazole)hexane, btbb = 1,4‐bis(thiabendazole)butane, 3‐H2npa = 3‐nitrophthalic acid and 5‐H2nipa = 5‐nitroisophthalic acid) were synthesized under hydrothermal conditions and characterized by physicochemical and spectroscopic methods as well as by single‐crystal X‐ray diffraction. Complex 1 features a fascinating meso‐helical chain, which is further extended into a 2D supramolecular framework involving π ··· π stacking interactions. Complexes 2 and 3 show dinuclear structures. Complex 2 is further connected through C–H ··· O hydrogen bonding interactions to afford a 2D supramolecular layer, whereas complex 3 is further extended to a rare 2‐nodal (3,4)‐connected supramolecular sheet with a point symbol of {3.42.5.6.7}2{3.82} by O–H ··· O hydrogen bonding interactions. The electrochemical behaviors of the two cobalt complexes 2 and 3 were reported. Moreover, the luminescent properties for 1 and the photocatalytic properties for the complexes were investigated.  相似文献   

13.

Reaction of potassium tetrachloroaurate(III), KAuCl4, with 2-pyridinecarboxaldehyde (2CHO-py) have been examined in protic HX (X=OH, OMe, OEt, OCH2CH2CH2, OCH2CH2CH2CH3, OCH2CF3) solvents. Compounds in which the pyridine ligand is N or N-O coordinated in a newly carbonyl hydrated or in semi- and acetal-forms, derived by addition of one or two hydroxylic molecules, have been isolated; these include dichloro[pyridine-2(α-hydroxymethanolato)]gold(III) (1), dichloro[pyridine-2(α-ethoxymethanolato)] gold(III) (2), dichloro[pyridine-2[α-(2,2,2-trifluoroethoxymethanolato)]gold(III) (3), trichloro(2-pyridinecarboxaldehyde dimethyl acetal)gold(III) (4), trichloro(2-pyridinecarboxaldehyde diethyl acetal)gold(III) (5), trichloro(2-pyridinecarboxaldehyde di-1-propyl acetal)gold(III) (6) and trichloro(2-pyridinecarboxaldehyde di-1-butyl acetal)gold(III) (7). The crystal and molecular structures of (2), (5) and (7) have been determined by X-ray methods. Compound (2) crystallizes in space group Pna21 with Z=4, a=7.8914(4), b=17.3660(4) and c=8.3873(5)Å; (5) crystallizes in space group P&1macr; with Z=2, a=7.7779(3), b=8.2878(2) and c=13.3202(6)Å, α=96.975(2), β=95.096(2), γ=115.027(2)°; (7) crystallizes in space group P21/a with Z=4, a=14.5438(12), b=8.9865(7) and c=15.0362(11)Å.  相似文献   

14.
Three new complexes, [Co(hfac)2(NIToPy)] (1), [CoCl2(NIToPy)2] (2), and [Co(NIToPy)3](ClO4)2 (3), with NIToPy = 2-(2-Pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-oxy-3-oxide, and hfac = hexafluoroacetylacetonate, have been synthesized. The compound 3 crystallized in the monoclinic space group P21, with two molecules in a unit cell of dimensions a = 10.565(4) Å, b = 14.714(9) Å, c = 14.596(7) Å, and β = 107.10(4)°. The temperature-dependent magnetic susceptibility measurements (4.2 K-300 K) for the complexes demonstrated strong antiferromagnetic exchange interaction between cobalt(II) ion and NIToPy radical spins with J = ?140.1 cm?1 for 1, J = ?94.2 cm?1 for 2, and J = ?161.8 cm?1 for 3, respectively. The magneto-structural correlation in these complexes has been discussed.  相似文献   

15.

Two diastereomers of bis(1,3-diaminopropane)(S-phenylalaninato)cobalt(III) were prepared by reaction of S-phenylalanine with carbonatobis(1,3-diaminopropane)cobalt(III). The diastereomers were separated on an optically active Sephadex QAE column and their absolute configurations assigned by means of circular dichroism. In addition, 1HNMR spectra of the diastereomers were analyzed in terms of the population of the three predominant rotamers of the coordinated S-phenylalaninato ligand. One out of 24 theoretically possible diastereomers of the dinuclear species di- µ -hydroxo- tetrakis(S-phenylalaninato)dicobalt(III) was obtained by direct synthesis and its absolute configuration deduced from CD spectra.  相似文献   

16.

Intra-molecular electronic energy transfer processes have been investigated in systems containing two distinct fluorophores Fl 1 (absorbing photonic energy) and Fl 2 (coumarin 343, brought at a close distance through coordinative interactions, emitting). Fl 1 is covalently linked or incorporated in a polyamine platform containing one or two Zn II ions, while Fl 2 coordinates the Zn II centre(s) through a carboxylate group. Zn II has been chosen for its photophysical inactivity and quick reversibility of the interaction with Fl 2 .  相似文献   

17.
报导了四个单核Co(Ⅱ)和Fe(Ⅱ)的配合物[Co(L1)2](ClO4)2·(CH3CN)(1),[Fe(L1)2](ClO4)2·(H2O)(2),[Co(L2)](ClO4)2(3),以及[Fe(L2)](ClO4)2·2H2O(4),(其中L1=4’-苯基-2,2’:6’,2”-三联吡啶,L2=N,N,N-三-(2-(2-吡啶甲叉氨基)乙基)胺)的合成和性质,以及配合物1、3的晶体结构.配合物1和3的晶体都属于单斜晶系.它们的晶胞参数分别为:1a=1.0855(4)nm,b=1.6201(5)nm,c=2.5236(5)nm,β=92.63(2)°,V=4.433(1)nm3;3a=2.8351(8)nm,b=1.0670(3)nm,c=1.9255(5)m,β=101.03(4)°,V=5717(2)nm3.2和4的氧化还原电位分别为E=0.78V和0.63V‘它们的d-d跃迁吸收最大值分别位于565和521nm处.  相似文献   

18.
Phosphoraneiminato Complexes of Nickel(II) with Heterocubane Structure The phosphoraneiminato complexes [NiBr(NPR3)]4 (R = CH3, C2H5) and [NiI(NPEt3)]4 were obtained from NiBr2 and NiI2, respectively, with excess Me3SiNPR3 in the melt (R = CH3, C2H5) in the presence of sodium fluoride. They form dark-green, moisture sensitive crystalline powders. They were characterized by IR spectroscopy, mass spectrometry, magnetic behaviour as well as by crystal structure analyses. The compounds possess heterocubane structures, in which the nickel atoms are linked via μ3–N-bridges of the phosphoraneiminato groups.  相似文献   

19.
Three new nickel(II) complexes constructed with N‐(2‐hydroxybenzyl)‐β‐alanine (H2L), namely [NiL(phen)H2O]·H2O ( 1 ) (phen = 1.10‐phenanthroline), [Ni4L4(H2O)4]·5H2O ( 2 ) and K[Ni4L4(NCS)(H2O)5]·5.42H2O ( 3 ) have been synthesized and characterized by single‐crystal X‐ray diffraction analysis. Complex 1 exhibits a discrete structure, and the structures are bound together through hydrogen bonding to a one‐dimensional chain in ladder‐like fashion. Complexes 2 and 3 contain similar [Ni42‐O)6] cores with “zig‐zig” arrangement. In complex 3 , the tetranuclear nickel units [Ni4L4(H2O)4] and [Ni4L4(NCS)(H2O)] are alternately bridged by potassium atoms to a one‐dimensional chain. The neighboring chains are further linked up by {K2O2} units to a two‐dimensional layer structure. Moreover, the IR, XRD, TGA and the temperature‐dependent magnetic susceptibility for 2 and 3 have also been studied.  相似文献   

20.
1 INTRODUCTIONInthepastfew years ,anincreasinginteresthasbeen giventothemagnetic propertiesofmolecularcomplexescomprisingsimultaneouslylanthanideandtransitionmetalionswiththeaimofclarifyingtheroleoftheexchangeinteractionsbetween 3dand 4fmetalionsmodifying…  相似文献   

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