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1.
A series of four mononuclear manganese (II) complexes with the N-tridentate neutral ligands 2,2′:6,2′′-terpyridine (terpy) and N,N-bis(2-pyridylmethyl)ethylamine (bpea) have been synthesized and crystallographically characterized. The complexes have five- to seven-coordinate manganese(II) ions depending on the additional ligands used. The [Mn(bpea)(Br)2] complex (1) has a five-coordinated manganese atom with a bipyramidal trigonal geometry, while [Mn(terpy)2](I)2 (2) is hexa-coordinated with a distorted octahedral geometry. Otherwise, the reactions of Mn(NO3)2 · 4H2O with terpy or bpea afforded novel seven-coordinate complexes [Mn(terpy)(NO3)2(H2O)] (3) and [Mn(bpea)(NO3)2] (4), respectively. 3 has a coordination polyhedron best described as a distorted pentagonal bipyramid geometry with one nitrate acting as a bidentate chelating ligand and the other nitrate as a monodentate one. 4 possesses a highly distorted polyhedron geometry with two bidentate chelating nitrate ligands. These complexes represent unusual examples of structurally characterized complexes with a coordination number seven for the Mn(II) ion and join a small family of nitrate complexes. 相似文献
2.
Iryna A. Koval Arno F. Stassen Martin Lutz Daniel Pursche Jan Reedijk 《Inorganica chimica acta》2004,357(1):294-300
The phenol-based compartmental ligand Hpy2ald contains a tridentate amino arm and a weak donor aldehyde group at the 2′ and at the 6′ positions of the phenol ring, respectively. This ligand reacts with cobalt(II) perchlorate, cobalt(II) tetrafluoroborate and manganese(II) perchlorate, yielding dinuclear complexes, where two metal ions are doubly bridged by two deprotonated cresolate moieties. The coordination environment around the metal ions is then completed to a very distorted octahedron by three nitrogen donor atoms from the pendant amino arm and the oxygen atom of the aldehyde group. The crystal structures of the complexes, their spectroscopic and magnetic properties are reported. 相似文献
3.
Subhendu Naskar Sumita Naskar Shyamal Kumar Chattopadhyay 《Inorganica chimica acta》2010,363(14):3641-18021
Five Ni(II) complexes of aroyl hydrazone ligands with 2,6-diacetyl pyridine monooxime are reported. X-ray crystal structure of the Ni(II) salicyloylhydrazone complex is also reported. In these complexes Ni(II) is in a distorted octahedral N4O2 coordination environment, with each of the two ligands coordinating through the pyridine nitrogen, imino-hydrazone nitrogen and the deprotonated oxygen of the hydrazone moiety. The iminooxime group remain uncoordinated in both the ligands and the planes containing the CH3-CN-OH groups are orthogonal to the adjacent pyridine rings. On excitation at 375 nm, the ligands as well as the Ni(II) complexes, show luminescence. However, the Ni(II) complexes have much lower quantum yield of emission than the free ligands. 相似文献
4.
Makoto Shimizu Fred Basolo Maria N. Vallejo Jack E. Baldwin 《Inorganica chimica acta》1984,91(4):251-255
Oxygen and NO binding constants are reported for Fe(Por)(B) [1] complexes. The results show a good correlation between O2 and NO affinities, and this is attributed to the similar bent structures of the FeOO and FeNO moieties. Evidence is presented to show that iron(II) C3-capped porphyrins have a low affinity for O2 because of ligand coordination on the cavity side of the cap. 相似文献
5.
Oleg V. Palamarciuc Paulina N. Bourosh Janusz Lipkowski Rodolphe Clérac 《Inorganica chimica acta》2010,363(11):2561-2566
The condensation of 2-formyl-pyridine with Girard’s T reagent yields a new hydrazone in the form of an ammonium quaternary salt: [H(2-PyGT)]Cl. This tridentate ligand is readily soluble in water and reacts with iron(III) or copper(II) chlorides to give [Fe(2-PyGT)Cl3] (1) or [Cu(2-PyGT)Cl2]·(H2O) (2) complexes, respectively. Single-crystal X-ray studies in 1 and 2 reveal that the coordination reaction gives rise to the deprotonation of the organic ligand that is coordinated using its NNO donor atoms in the form of a zwitterion species. The coordination spheres around the transition metal ions in complexes 1 and 2 are quite different. In 1, the iron site adopts a distorted octahedral coordination sphere, while the Cu(II) ions in 2 show a distorted tetragonal-pyramid geometry. As expected, the magnetic properties of these compounds reveal only weak antiferromagnetic interaction between spin carriers. 相似文献
6.
《Inorganica chimica acta》1988,146(1):93-97
The coordination of 2-cyanopyridine molecule to Ni(II) atom promotes a nucleophilic addition of solvent molecules (water, methanol, ethanol) to the nitrile group. The addition of water leads to the formation of solid complexes containing pyridine-2- carboxamide as a chelate ligand. An analogous reaction of 2-cyanopyridine with NiX2 (X = Cl, Br, I, NCS) in methanolic solutions gives, however, complexes containing two or three molecules of O-methylpyridine-2-carboximidate. No nucleophilic addition of solvent occurred with 3- and 4-cyanopyridine under the same reaction conditions.The complexes under study exhibit an octahedral geometry. The structure and the mode of the ligand coordination have been determined by IR spectra. 相似文献
7.
Robert Bronisz 《Inorganica chimica acta》2004,357(2):396-404
A series of new coordination polymers of Cu(II) have been prepared in a reaction between copper(II) perchlorate or tetrafluoroborate salt and a novel ligand 1,4-di(1,2,3,4-tetrazol-2-yl)butane (bbtz). The compounds were characterised by an elemental analysis, TG measurements, IR, EPR and UV-Vis spectroscopy. Crystal structures of bbtz and five complexes of Cu(II) were determined by a single crystal X-ray diffraction measurement performed at 100 K. The composition and architecture of the obtained complexes strongly depend on the reaction conditions especially on the kind of solvent. Investigated complexes are composed of polymeric macrocations and non-coordinated anions. In all cases the bbtz molecules act as the bidentate ligand coordinated to metal(II) ions via N4, N4′ nitrogen atoms from tetrazole rings. The complexes {[Cu(bbtz)2(MeOH)2]X2}∞ (X=ClO4−, BF4−) crystallise from methanol as 2D coordination polymers. In these compounds central metal ions are coplanar linked by molecules of bbtz and a coordination sphere is completed by axially coordinated solvent molecules. The complexes {[Cu(bbtz)3]X2}∞ (X=ClO4−, BF4−) were synthesised in EtOH/H2O solvent system and posses a common network topology. In this group of complexes each central atom is linked by ligand molecules to six other in plane arranged central atoms resulting in 2D networks. Reactions between Cu(II) salts and bbtz performed in absolute ethanol resulted in the formation of the next type of product. In {[Cu(bbtz)3](ClO4)2·2EtOH}∞ neighboured copper(II) ions are linked by ligand molecules in the three directions what leads to the formation of 3D net. A crystal of this complex is composed of two mutually interpenetrated 3D networks. 相似文献
8.
Tippu S Sheriff Pamela Carr Michael B Hursthouse Mark E Light 《Inorganica chimica acta》2004,357(9):2494-2502
The mononuclear complexes (Bu4N)[Mn(Cl4Cat)2(H2O)(EtOH)] and (Bu4N)2[Mn(Cl4Cat)3] (H2Cat=1,2-dihydroxybenzene) have been synthesised and characterised by X-ray diffraction. This work provides a direct, independent, synthesis of these complexes and an interesting example of how solvent effects can promote the formation of either a manganese(III) or manganese(IV) complex of the same ligand. The characterisation of (Bu4N)[Mn(Cl4Cat)2(H2O)(EtOH)] supports previous work that manganese(III) is extremely reluctant to form tris (catecholato) complexes due to the short `bite distance' of catecholate oxygen atoms (2.79 Å) which are unable to span the elongated coordination axes of the Jahn-Teller distorted Mn(III) ion and explains the 2:1 and 3:1 tetrachlorocatechol:manganese ratios in the Mn(III) and Mn(IV) complexes, respectively. Hydrogen peroxide production using dioxygen and hydroxylamine as substrates in acetonitrile/water mixtures, under ambient conditions, can be demonstrated with both complexes, suggesting that neither labile coordination sites nor the oxidation state of the manganese are important to the catalytic system. Turn over frequencies (TOF, moles of H2O2 per moles of manganese per hour) of ∼10 000 h−1 are obtained and this compares very favourably with the commercial production of hydrogen peroxide by the autoxidation of 2-ethylanthrahydroquinone (AO process). 相似文献
9.
Marta Sobiesiak Agnieszka Mrozek Ingo-Peter Lorenz Urszula Krajewska 《Inorganica chimica acta》2010,363(10):2171-3244
1-Benzothiazol-2-yl-3,5-dimethyl-1H-pyrazole (1a) and 1-benzothiazol-2-yl-5-(2-hydroxyphenyl)-3-methyl-1H-pyrazole-4-carboxylic acid methyl ester (1b) were reacted with the hexahydrates of cobalt(II) chloride, cobalt(II) nitrate and cobalt(II) perchlorate to give the corresponding complexes 2a-4a and 2b-5b, respectively. Obtained compounds differ in coordination spheres of central atoms. The complex 2a includes a fivefold coordinated cobalt(II) ion, whereas 3a shows a distorted octahedral configuration around the cobalt(II) ion. All complexes were characterised by FTIR spectroscopy, MS and elemental analysis. The X-ray structures of 2a, 3a and 5b complexes were also solved. The cytotoxic properties of the ligand 1a and both series of Co(II) complexes were examined on human leukemia NALM-6 and HL-60 cells and melanoma WM-115 cells. The ligands, were found to have very low cytotoxicity. Complex 3b exhibited the highest cytotoxic activity with IC50 values in the range of 6.9-17.1 μM for three examined cell lines. 相似文献
10.
John M. Bellerby John H. Morris W.Ewen Smith James M. McCrae 《Inorganica chimica acta》1985,96(2):209-212
Mononuclear Zn(II) and Ni(II) complexes have been prepared from two new Schiff base ligands in which two alternative co-ordination sites (N2O2 or O2O2) occur. The first ligands is the Schiff base derived from 1,2-diaminobenzene and 2-hydroxy-3-carboxyl-1-napthaldehyde (bopaH4). The complexes of this ligand contain the metal ions in the N2O2 coordination site as a result of the steric requirements of the co-ordinated ligand. The second ligand series are derivatives of X-substituted 1,2-diaminobenzenes, 2-hydroxy-3-carboxy-1-naphthaldehyde and 2-hydroxy-5-methyl isophthaldehyde (X-bolaH3). In this case Ni(II) occupies the N2O2 site in its complexes with the X-bolaH3 ligands, whereas the Zn(II) complexes are co-ordinate through the O2O2 site since the steric restrictions are less severe. 相似文献
11.
Hassan Keypour Parisa Arzhangi Majid Rezaeivala Hamid Reza Khavasi 《Inorganica chimica acta》2011,367(1):9-2895
A new potentially tetradentate (N4) Schiff base ligand (L), 1,9,12,20-tetraazatetracyclo[18.2.2.02,7.014,19]tetracosa-2(7),3,5,8,12,14(19),15,17-octaene containing a piperazine moiety is described. Macrocyclic Schiff base complexes, [NiL](ClO4)2 (1) and [CuL](ClO4)2 (2) have been obtained from equimolar amounts of ligand (L) with nickel(II) and copper(II) metal ions. While the equilibrium reaction in the presence of cobalt(II) and zinc(II) metal ions with ligand L in a 1:1 molar ratio yielded the open-chain Schiff base complexes, [CoL′](ClO4)2 (3) and [ZnL′](ClO4)2 (4) containing two terminal primary amino groups. The ligand L′ is 1,4-bis(2-(2-aminoethyliminomethyl)phenyl)piperazine. The crystal structures of (1) and (4) have been also determined by X-ray diffraction. It was shown that the Ni(II) is coordinated to the ligand L by two nitrogen atoms of piperazine group and two nitrogen atoms of the imine groups, in a slightly distorted square-planar geometry. Also single crystal X-ray analysis of (4) confirmed a distorted octahedral arrangement in the vicinity of Zn atom with N6 donor set. The spectroscopic characterization of all complexes is consistent with their crystal structures. 相似文献
12.
The new hexadentate, bis-pincer ligand, (dipyCH2)MeNCH2CH2NMe(CH2dipy) (dipy = 2,2′-dipyridyl-6-yl) forms a crystallographically characterized Mn(II) complex in which each half of the ligand binds a separate Mn(OAc)2 unit. The structure consists of a distorted N3Mn(η2-OAc)(η1-OAc) core with six normal coordinate bonds and a long (2.85 Å) secondary bond to a seventh ligand atom, an oxygen of the η1-acetate. In addition to demonstrating an interesting coordination mode, the structure also mimics a predicted transition state in the associative ligand exchange of octahedral Mn(II) complexes. 相似文献
13.
Marina Porchia Grazia Papini Giancarlo Gioia Lobbia Francesco Tisato Alessandro Dolmella 《Inorganica chimica acta》2006,359(8):2501-2508
Ligand-exchange reactions of bidentate donor agents such as malonic acid (H2mal) or 1,3-propanediol (H2diol) with labile Re(O)(bdmpza)Cl2 (bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate) precursors in the presence of triethylamine yield the mixed-ligand complexes Re(O)(bdmpza)(mal) (2) and Re(O)(bdmpza)(diol) (3), respectively. Compounds 2 and 3 can also be obtained starting directly from [Re(O)Cl4][NBu4], Libdmpza and the appropriate bidentate ligand in the presence of triethylamine. X-ray analyses of the two compounds show in both cases a distorted octahedral geometry around the rhenium atom comprising two pyrazolyl nitrogens and the bidentate ligand in the equatorial plane, and the oxo and the carboxylate oxygens on the apices. Differently from 2 and 3, X-ray diffraction analysis of the asymmetric precursor (OC-6-42)Re(O)(bdmpza)Cl2 (1) reveals a slightly distorted octahedral geometry with the apical positions taken by the carboxylate oxygen and a chloride atom, and with the equatorial plane occupied by the nitrogens of the bis-pyrazolyl ligand, a chloride and the oxygen atom. 相似文献
14.
Vinod P. Singh Shweta Singh Anshu Katiyar 《Journal of enzyme inhibition and medicinal chemistry》2013,28(2):577-588
Complexes of the type [M(pabh)(H2O)Cl], [M(pcbh)(H2O)Cl] and [M(Hpabh)(H2O)2 (SO4)] where, M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); Hpabh = p-amino acetophenone benzoyl hydrazone and Hpcbh = p-chloro acetophenone benzoyl hydrazone have been synthesized and characterized with the help of elemental analyses, electrical conductance, magnetic susceptibility measurements, electronic, ESR and IR spectra, thermal (TGA & DTA) and X-ray diffraction studies. Co(II), Ni(II) and Cu(II) chloride complexes are square planar, whereas their sulfate complexes have spin-free octahedral geometry. ESR spectra of Cu(II) complexes with Hpabh are axial and suggest as the ground state. The ligand is bidentate bonding through >C = N ? and deprotonated enolate group in all the chloro complexes, whereas, >C = N and >C = O groups in all the sulfato complexes. Thermal studies (TGA & DTA) on [Cu(Hpabh)(H2O)2(SO4)] indicate a multistep decomposition pattern, which are both exothermic and endothermic in nature. X-ray powder diffraction parameters for [Co(pabh)(H2O)Cl] and [Ni(Hpabh)(H2O)2(SO4)] correspond to tetragonal and orthorhombic crystal lattices, respectively. The ligands as well as their complexes show a significant antifungal and antibacterial activity. The metal complexes are more active than the ligand. 相似文献
15.
Patrick GamezRosienne H Steensma Willem L Driessen Jan Reedijk 《Inorganica chimica acta》2002,333(1):51-56
The tridentate ligand 2,6-bis(pyrazol-3-yl)pyridine (dPzPy) renders coordination compounds with halide, nitrate and tetrafluoroborate salts of copper. The complexes, which have the form [Cu(dPzPy)X2] with X=Br and Cl, [Cu(dPzPy)(NO3)2](H2O), and [Cu(dPzPy)2](BF4)(SiF6)0.5(MeOH)3 have been characterized by elemental analysis and by IR, EPR and ligand field spectroscopy. The single-crystal X-ray structure of [Cu(C11H9N5)Br2] shows the copper(II) ion to be coordinated by three N atoms of 2,6-bis(pyrazol-3-yl)pyridine and two bromides in a geometry exactly in between a trigonal-bipyramid and a square-pyramid. Each molecule lies on a crystallographic C2-symmetry axis. They are coupled to one another by a two-dimensional network through NH to Br hydrogen bonds. The crystal structure of [Cu(C11H9N5)Cl2] is analogous to the bromide. The single-crystal X-ray structure of [Cu(dPzPy)2](BF4)(SiF6)0.5(MeOH)3 shows the copper ion to be in a Jahn-Teller distorted octahedral N6 environment of two mer-oriented tridentate ligands. 相似文献
16.
Two novel coordination polymeric complexes [Co(pzca)2(H2O)]n (1) and [Mn(pzca)2]n (2) (pzca=2-pyrazinecarboxylate) have been synthesized by hydrothermal reaction of M(CH3COO)2·4H2O (M=Co, Mn) and 2-pyrazinecarboxylic acid. The complex 1 displays an infinite zigzag chain structure in which each cobalt(II) center was coordinated by three nitrogen and three oxygen atoms to generate a CoN3O3 octahedral geometry. The existence of hydrogen bond leads to the formation of the interpenetrating stacking structure. Complex 2 indicates a two-dimensional layer structure through the linkage of bridging oxygen atom of pzca ligand. Each Mn(II) center exhibits a distorted octahedral coordination environment with four oxygen atoms and two nitrogen atoms. The distances of adjacent Mn(II) atoms are 3.503 and 5.654 Å, respectively. The magnetic property analyses reveal that both complexes show weak antiferromagnetic exchange interactions between the metal centers. 相似文献
17.
Copper(II), cobalt and nickel(II) complexes of tris(benzimidazolylmethyl)amine(1) and of its methyl(2), isobutyl(3) or isopropyl(4)-substituted derivatives of one of the backbone methylene groups were prepared and characterized. The ligands (1)–(3) afforded trigonal bipyramidal copper(II) complexes, whereas ligand (4) gave a tetrahedrally distorted tetragonal one because of the steric hindrance arising from the isopropyl group. All the cobalt(II) complexes prepared were supposed to be tetrahedral or pseudotrigonal bipyramidal, and all the nickel(II) complexes to be slightly tetrahedrally distorted octahedral. Ternary copper(II) systems containing several thiolates as the third component exhibited intense blue, brown or green color under a reduced temperature by virtue of the charge transfer bands, S? → Cu. 相似文献
18.
《Inorganica chimica acta》2004,357(5):1457-1464
We have carried out the synthesis of the cadmium coordination compounds [Cd(NO3)2(PyTT)(H2O)] (1) and [CdCl2{(μ-Cl)2CdCl(μ-Cl)(μ-PyTT)Cd}2]n (2), together with their structural determination by means of X-ray diffraction. The compounds were also characterized through elemental analysis and infrared spectroscopy. The first complex presents a distorted pentagonal bipyramidal geometry with the axial positions occupied by one oxygen atom from a water molecule and a second one from a nitrate ion which acts as a monodentate ligand, whereas the equatorial plane contains three nitrogen atoms from the organic moiety and two oxygen atoms coming from the other nitrate group, which is bidentate. The structure of the second complex consists of parallel sheets linked by van der Waals forces, each one made up of structural units [CdCl2{(μ-Cl)2CdCl(μ-Cl)(μ-PyTT)Cd}2], which possesses two PyTT ligands, 10 bridging chloro ligands and 5 cadmium(II) centres belonging to three environment types: octahedral CdN2Cl4, octahedral CdCl6, on which a centre of symmetry is located, and tetrahedral CdNCl3, present in a 2:1:2 ratio. 相似文献
19.
A new dinuclear manganese(II)-azido complex: [Mn(2,2′-dpa)(N3)2]21 (2,2′-dpa = 2,2′-dipicolylamine) has been synthesized solvothermally. X-ray crystallography analysis reveals that it consists of two crystallographically independent dimeric manganese moieties; each manganese(II) atom is coordinated by one 2,2′-dipicolylamine, one terminal azido ligand, and double end-on bridging azido ligands, exhibiting a slightly distorted octahedral sphere. There are extensive short contacts among dimeric manganese moieties, which extend the structure into an interesting three-dimensional supramolecular array. Magnetic determination of 1 indicates that dominant ferromagnetic interaction and weak antiferromagnetic interaction, which are ascribed to the end-on azido bridges and the short contacts, respectively, co-exist in this complex. 相似文献
20.
Reactions of silver(I) perchlorate with tetraphenyl-cyclopentadiene (Ph4H2C5) have isolated two novel silver(I) bridged tetraphenyl-pyrylium complexes: [Ag(ClO4)(Ph4HC5O+)](ClO4)− (1) and (2), depending on moisture-content of the reactants. Structure studies using single-crystal X-ray diffraction have showed that complex 1 contains a distorted tetrahedral metal center bridging two neighboring peripheral phenyl rings of one pyrylium cation and two perchlorate anions, whereas 2 involves a three-coordinate metal ion interacting with a pair of phenyl rings and one water molecule, leaving two perchlorate anions free from coordination. For both complexes, the precursor ligand Ph4H2C5 undergoes a ring-enlargement reaction, forming a six-membered pyrylium cation. The fundamentals of the synthesis, structure characterization and some properties are discussed. 相似文献