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1.
Bis[1,2-bis(4-methylphenyl)ethanedione dioximato]nickel(II), [Ni{(C1)2dpg}2] (1), was found to exhibit shift in diffuse reflectance spectra from the corresponding non-methyl species. Characterization by X-ray crystal structural analysis on 1 and bis[1,2-bis(4-n-hexylphenyl)ethanedione dioximato]nickel(II), [Ni{(C6)2dpg}2] (2), revealed the presence of the edge-to-face aromatic interactions caused by the electron-donating effect of the methyl and hexyl groups. The Ni(dpg)2 units of complex 2 stack (staggered by 90°) at alternate intervals of 3.151 Å and 3.253 Å. Thus, the shift in the d-p transition of 2 was found to contain 43% of the effect of the edge-to-face aromatic interaction, together with 57% of the reported fastener effect. 相似文献
2.
Edward Sz?yk Andrzej Wojtczak Andrzej Surdykowski Marcin Go?dzikiewicz 《Inorganica chimica acta》2005,358(3):467-475
Schiff bases obtained from (1R,2R)-(−)-cyclohexanediamine and 5-chloro- (1) or 5-bromosalicylaldehyde (2) are used as ligands for Zn(II) resulting in [(1R,2R)-cyclohexylenebis(5-chlorosalicylideneiminato)]zinc(II) (1a) and (1R,2R)-[cyclohexylenebis-(5-bromosalicylideneiminato)]zinc(II) (2a). In the presence of pyridine, 1a and 2a turned out into (1R,2R)-[cyclohexylenebis(5-chlorosalicylideneiminato)pyridine]zinc(II) (1b) and (1R,2R)-[cyclohexylenebis(5-bromosalicylideneiminato)pyridine]zinc(II) (2b). Coordination sphere of Zn(II) atoms in both pyridine adducts is a slightly distorted square pyramid, with N2O2 chromophore units and axially bonded pyridine as it is evident from single crystal X-ray analyzes of 1b and 2b. The asymmetric unit of 1b and 2b contains two molecules of complexes. The observed distances of Zn-O in both molecules indicate the rigidity of the tetradentate ligand as a main factor influencing the geometry of coordination sphere. Obtained complexes were characterized by 1H NMR in solution and 13C CP MAS NMR. NOE differential experiments revealed significant steric interactions between C(6)-H in the phenyl ring, cyclohexyl C(1)-H and imine hydrogen. Significant coordination shifts of carbons in the closest proximity to the coordination center were noted as well. 相似文献
3.
Ahmet Karada? Ay?egül ?enocak Yusuf Yerli A. Cemil Ba?aran 《Inorganica chimica acta》2009,362(7):2299-278
Two unique bimetalic Pt(II) coordination polymers of composition [Ni(hydeten)2Pt(CN)4] (Ni-Pt) and [Cu(hydeten)2Pt(CN)4] (Cu-Pt) [hydeten = N-(2-hydroxyethyl-ethylenediamine) or 2-(2-aminoethylamino)ethanol] have been synthesized and structurally characterized by various methods in this study. The crystal structure of Cu-Pt was determined by single-crystal X-ray diffraction analysis. The structure of Cu-Pt forms of infinite 2,2-TT type [-Cu(hydeten)2-NC-Pt(CN)2-CN-] chains containing paramagnetic copper atoms bridged by tetracyanoplatinate species. In this complex, Cu(II) centers display an axially elongated octahedron with two chelating hydeten molecules in the equatorial positions and N-bonded bridging cyano groups in the axial positions, whereas Pt(II) centers are four coordinate with four cyanide-carbon atoms in a square-planar arrangement. The decrease of the moments of these complexes in temperature range of 50 305 K can assigned to the antiferromagnetic interactions in the structures. The thermal decomposition of Cu-Pt comprise of five distinguished stages, while the thermal decomposition of Ni-Pt take place four different stages. 相似文献
4.
Reaction of the potassium salt of the N-thiophosphorylthiourea H2NC(S)NHP(S)(OiPr)2 (HL) with Co(II), Ni(II), Zn(II) and Cd(II) cations in aqueous EtOH leads to the chelate complexes [ML2] all showing a 1,5-S,S′-coordination formed by the CS and PS sulfur atoms of two deprotonated ligands L−. The structures of the resulting compounds were studied by IR, UV-Vis, 1H, 31P{1H} NMR spectroscopy and microanalysis. The metal center is found in a tetrahedral environment in [CoL2], [ZnL2] and [CdL2]. According to NMR and UV-Vis spectroscopy the metal cation of [NiL2] exhibits square planar coordination geometry in CH2Cl2, CHCl3 and C6H6, while tetrahedral geometry is observed in acetone, DMSO and DMF. Regardless of the solvent used for the crystallization of [NiL2], the molecular structure in the solid is always square planar as was confirmed by XRD of single crystals and magnetic measurements of the polycrystalline material. The magnetic and photoluminescent properties of all complexes are also reported. 相似文献
5.
Peiju Yang Cui Zhang Xiao-Juan Yang Huai-Ming Hu Biao Wu 《Inorganica chimica acta》2009,362(1):89-3592
A series of nickel(II) and cobalt(II) complexes, NiX2L (X = Cl, Br; 1-6) and CoCl2L (7-9), with 2,9-diaryl-1,10-phenanthroline ligands (L1-L3) have been synthesized and characterized by elemental analysis, UV-Vis, IR spectroscopy, and X-ray crystal structural study (for 1, 4-7, 9). The solid-state structures of 1, 5-7 and 9 show four-coordinate, slightly flattened tetrahedral geometry at the Ni(II) or Co(II) center, while 4 is five-coordinated (square-pyramidal), containing a THF molecule as an auxiliary ligand. The title complexes (1-9) display good catalytic activities in ethylene oligomerization when activated with methylaluminoxane (MAO). While the Co(II) precatalysts produce primarily C4 isomers, the Ni(II) complexes give ethylene dimers and trimers at normal pressure. The activities and yields of linear α-olefins increase with increasing ethylene pressure for the Ni(II) complexes, leading to more high-molar-mass products (C8-C18). Complex 6 displays the best catalytic activity among the complexes studied (up to 1518 kg/mol[Ni] h at 10 atm). 相似文献
6.
The coordination chemistry of the ligand bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]ether (L1) was tested in front of Pd(II) and Pt(II). Complexes cis-[MCl2(L1)] (M=Pd(II) and Pt(II)) were obtained, due to the chelate condition of the ligand and the formation of a stable 10-membered ring. The crystal structure of cis-[PtCl2(L1)] was resolved by X-ray diffraction. Treatment of [PdCl2(L1)] or [Pd(CH3CN)4](BF4)2 with AgBF4 in the presence of L1 gave the complex [Pd(L1)2](BF4)2. The initial cis-[PdCl2(L1)] was recovered by reacting [Pd(L1)2](BF4)2 with an excess of NEt4Cl. Reaction of [Pt(CH3CN)4](BF4)2 (generated in situ from [PtCl2(CH3CN)2] and AgBF4 in acetonitrile) with ligand L1 yields complex [Pt(L1)2](BF4)2. 相似文献
7.
Katsura Mochizuki Tomoko Sugita Fumi Yamada Yasunobu Ohgami Syouhei Kato 《Inorganica chimica acta》2010,363(13):3151-3157
New nickel(II) complexes with macrocyclic ligands bearing benzyloxy [(5), (9)], 2-methylbenzyloxy (7), 3-methylbenzyloxy (8), and hydroxy (6) groups on the pyridine ring have been synthesized. Structures of the hydroxy substituted macrocyclic ligand (L-OH·3HCl·H2O), and the benzyloxy substituted ligand (L-OBn·3HCl) and its nickel(II) complex (5), as well as an analogous Ni(II) complex (8), have been revealed by X-ray crystallography. Their catalytic capabilities in the reductive debromination of 1-bromo-4-tert-butylbenzene have been elucidated, which has revealed that the pyridine ring can be a suitable position for the introduction of functional groups while maintaining the catalytic capabilities of the nickel(II) complexes. 相似文献
8.
Xian-He Bu He LiuMiao Du Keith Man-Chung WongVivian Wing-Wah Yam 《Inorganica chimica acta》2002,333(1):32-40
The complexes of Cu(I), Cu(II), Ni(II), Zn(II) and Co(II) with a new polypyridyl ligand, 2,3-bis(2-pyridyl)-5,8-dimethoxyquinoxaline (L), have been synthesized and characterized. The crystal structures of these complexes have been elucidated by X-ray diffraction analyses and three types of coordination modes for L were found to exist in them. In the dinuclear complex [Cu(I)L(CH3CN)]2·(ClO4)2 (1), L acts as a tridentate ligand with two Cu(I) centers bridged by two L ligands to form a box-like dimeric structure, in which each Cu(I) ion is penta-coordinated with three nitrogen atoms and a methoxyl oxygen atom of two L ligands, and an acetonitrile. In [Cu(II)L(NO3)2]·CH3CN 2, the Cu(II) center is coordinated to the two nitrogen atoms of the two pyridine rings of L which acts as a bidentate ligand. The structures of [Ni(II)L(NO3)(H2O)2]·2CH3CN·NO3 (3), [Zn(II)L(NO3)2 (H2O)]·2CH3CN (4) and [Co(II)LCl2(H2O)] (5) are similar to each other in which L acts as a tridentate ligand by using its half side, and the metal centers are coordinated to a methoxyl oxygen atom and two bipyridine nitrogen atoms of L in the same side. The formation of infinite quasi-one-dimensional chains (1, 4 and 5) or a quasi-two-dimensional sheet (2) assisted by the intra- or intermolecular face-to-face aryl stacking interactions and hydrogen bonds may have stabilized the crystals of these complexes. Luminescence studies showed that 1 exhibits broad, structureless emissions at 420 nm in the solid state and at 450 nm in frozen alcohol frozen glasses at 77 K. Cyclic voltammetric studies of 1 show the presence of an irreversible metal-centered reduction wave at approximately −0.973 V versus Fc+/0 and a quasi-reversible ligand-centered reduction couple at approximately −1.996 V versus Fc+/0. The solution behaviors of these complexes have been further studied by UV-Vis and ESR techniques. 相似文献
9.
The nickel(II) complexes of the compositions [Ni(hmidtc)(bpy)2]ClO4 (I), [Ni(hmidtc)(phen)2]ClO4 (II), [Ni(hmidtc)(phen)2]SCN (III), [Ni(hmidtc)(phen)2]PF6 (IV), [Ni(hmidtc)(phen)2]BPh4 (V), [Ni(hmidtc)(phen)2]AcO·2H2O (VI) and [Ni(hmidtc)(phen)2]Br·H2O (VII), involving a combination of one hexamethyleneimine-dithiocarbamate anion (hmidtc) and two bidentate N,N-donor ligands (2,2′-bipyridine (bpy) for I or 1,10-phenanthroline (phen) for II-VII), have been prepared. The compounds were characterized by elemental analysis, molar conductivity measurements, UV-Vis and IR spectroscopy, magnetochemical measurements and thermal analysis. A single-crystal X-ray analysis of the complex I revealed a distorted octahedral geometry with the nickel(II) ion coordinated by four nitrogen atoms (from two bidentate-coordinated bpy molecules) and two sulfur atoms (from one bidentate-coordinated hmidtc anion), together giving an NiN4S2 donor set. 相似文献
10.
Reaction of [NiCl2(dtbpe)] (dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) with one equivalent of NaBArF4 (BArF4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) gives the dinuclear chloro-bridged nickel complex [Ni2(μ-Cl)2(dtbpe)2](BArF4)2 (1). [Ni(solv)6](BF4)2 reacts with dtbpe to give, depending on the solvent, the fluoro-bridged complex [Ni2(μ-F)2(dtbpe)2](BF4)2 (2) (solv = THF) or the mononuclear chelate complex [Ni(MeCN)2(dtbpe)](BF4)2 (3) (solv = MeCN). In 1-3, nickel cations are coordinated in a square-planar fashion according to X-ray crystallography. No Ni-Ni interaction was observed in dinuclear halogen-bridged complexes 1 and 2. 相似文献
11.
Zala Mahendrasinh Sujit B. Kumar Albert Escuer E. Suresh 《Inorganica chimica acta》2011,375(1):333-337
Binuclear cyanate bridged nickel(II) complex [Ni(L)(NCO)]2(PF6)2 (1) and copper(II) complex [Cu(L)(NCO)]2(PF6)2 (2), where L is N,N-bis(3,5-dimethylpyrazol-1-ylmethyl)aminomethylpyridine, a tetradentate N4-coordinated ligand have been synthesized and characterized by physicochemical method. The structures of complexes 1 and 2 have been studied by single crystal X-ray diffraction analysis. The structure analysis reveals that both nickel(II) and copper(II) center are coordinated in distorted octahedral fashion and coordination mode of cyanate ligand is end-to-end (μ-1,3) for complex 1 but it is double end-on (μ-1,1) mode for complex 2. The variable temperature magnetic susceptibility data, measured from 2 to 300 K, show weak antiferromagnetic interaction with J value −6.2(1) cm−1 for complex 1, whereas complex 2 has very weak ferromagnetic interaction with J value +0.5(1) cm−1. 相似文献
12.
A series of Ni(II) and Cu(II) complexes of the hexaaza macrocycles, 3,6,9,17,20,23-hexaazatricyclo[23.3.1.111,15]triaconta-1(29),11(30),12,14,25,27-hexaene (L1) and 3,6,9,16,19,22-hexaazatricyclo[22.2.2.211,14]triaconta-1(26),11(29),12,14(30),24(28),25-hexaene (L2), have been prepared and the crystal structures determined for [Ni2L1(O2CCH3)2(H2O)2](ClO4)2 (1), [Ni2L2(DMF)6](ClO4)4 · 2H2O (2), {[Cu2L2Br(O2CCH3)](ClO4)2}n (3), [Cu2L2(μ-CO3)(H2O)2]2(ClO4)4 · 8H2O (4), [Cu2L2(O2CCH3)2](BF4)2 (5), and [Cu2L1(μ-imidazolate)Br]2Br4 · 6H2O (6). In these complexes, two metal centers are bound per ligand; in 1 and 3-6, the N3 subunits of L1 or L2 coordinate meridionally to the metal centers, whilst in 2, each N3 subunit in L2 adopts a facial mode of coordination. The binuclear cations in 1 and 2 have chair-like conformations, with the distorted octahedral Ni(II) coordination spheres completed by terminal water and a bidentate acetate ligand in 1 and three DMF ligands in 2. The Cu(II) centers in 3-6 generally reside in square planar environments, although a weakly binding ligand enters the coordination sphere in some cases, generating a distorted square pyramidal geometry. The binuclear [Cu2L2]4+ units in 3, 4 and 5 adopt similar bowl-shaped conformations, stabilized by H-bonding interactions between pairs of amine groups from L2 and a perchlorate or tetrafluoroborate anion. In 3, the binuclear units are linked through acetate groups, bridging in a syn-anti fashion, to produce a zig-zag polymeric chain structure, whilst 4 incorporates a tetrameric cation consisting of two binuclear units linked via a pair of carbonate bridges. Compound 6 features an imidazolate bridge between the two Cu(II) centers bound by L1. Pairs of [Cu2L1(μ-imidazolate)]3+ units are then weakly linked through a pair of bromide anions. 相似文献
13.
The dinuclear terephthalato-bridged nickel(II) complexes [Ni2(cyclen)2(μ-tp)](ClO4)2 (1) [Ni2(trpn)2(μ-tp)(H2O)2](ClO4)2 (2) and [Ni2(3,3,3-tet)2(μ-tp)(H2O)2](ClO4)2 · 2H2O (3), where tp = terephthalate dianion, cyclen = 1,4,7,10-tetraazacyclododecane, trpn = tris(3-aminopropyl)amine and 3,3,3-tet = 1,5,9,13-tetraazatridecane, were synthesized and structurally characterized by X-ray crystallography. Their magnetic susceptibilities were also determined at variable temperatures over the range 2-300 K. The structures of these complexes consist of μ-tp bridging two Ni(II) centers in a bis(bidentate) bonding fashion in 1 and in bis(monodentate) bonding fashion in 2 and 3. The coordination geometry around the Ni(II) ions in these compounds has a distorted octahedral geometry with four nitrogen atoms from the amine ligand (cyclen, trpn or 3,3,3-tet) and two coordinated oxygen atoms supplied by the chelated carboxylate group of the bridged terephthalate ligand in 1, and by one tp-carboxylate-oxygen in 2 and 3. The sixth coordination site in the last two complexes 2 and 3 is achieved via an oxygen atom from a coordinated water molecule. The intradimer Ni…Ni distances in these complexes are 10.740, 11.428 and 11.537 Å for 1, 2 and 3, respectively. The electronic spectra of the complexes in aqueous solutions are in complete agreement with the assigned X-ray geometry around the Ni(II) centers. Also, the analysis of the infrared spectral data for the ν(COO−) stretching frequencies of the tp-carboxalato groups reveals the existence of the bis(bidentate) and bis(monodentate) coordination modes for the bridged terephthalate ligand in 1, 2 and 3, respectively. Despite the different coordination modes of the tp bridging ligand in these complexes, they all exhibit very weak antiferromagnetic coupling. The coupling constants J were found to be −2.2, −0.6 and −1.5 cm3 K mol−1 for the complexes 1, 2 and 3, respectively. The structural and magnetic results of 1-3 are discussed in relation to the other related published μ-terephthalato dinuclear Ni(II) compounds. 相似文献
14.
Ramababu Bolligarla 《Inorganica chimica acta》2010,363(12):3061-3069
The syntheses, crystal structures and properties of compounds [Bu4N]2[Ni(ppdt)2] (1) and [Bu4N]2[Pt(ppdt)2] (2) (ppdt = pyrido[2,3-b]pyrazine-2,3-dithiolate) have been described. Compound 1 crystallizes in P21/c space group (monoclinic system), whereas compound 2 crystallizes in C2/c space group (monoclinic system). The crystal structures of both compounds 1 and 2 have been characterized by C-H?S and C-H?N hydrogen bonding interactions between cation and anions resulting in three-dimensional supramolecular networks in the crystals of 1 and 2, respectively. The acid-base behavior of the ground states of both [Bu4N]2[Ni(ppdt)2] (1) and [Bu4N]2[Pt(ppdt)2] (2) and also the excited state of compound [Bu4N]2[Pt(ppdt)2] (2) in solutions has been studied. The pH dependent changes in the charge transfer absorption and emission spectra are attributed to the protonation on an imine nitrogen of the ppdt ligand. The ground-state basicity constants of the two complexes 1 and 2 have been determined from spectrophotometric analysis by titrating with an weak acid, yielding pKb1 = 8.0 for complex [Bu4N]2[Ni(ppdt)2] (1) and pKb1 = 7.8 for complex [Bu4N]2[Pt(ppdt)2] (2). The excited-state basicity constant pKb1* for complex [Bu4N]2[Pt(ppdt)2] (2) has been determined by a thermodynamic equation using a Förster analysis yielding the value of 1.8. The complex 2 is electrochemically irreversible with an oxidation potential of E1/2 = +0.41 V versus Ag/AgCl in methanol. 相似文献
15.
Miklós Czaun Simphiwe M. Nelana Ilia A. Guzei Mikael Håkansson George Lisensky Ebbe Nordlander 《Inorganica chimica acta》2010,363(12):3102-3112
The reactions of six diimine ligands with Cu(II) and Ni(II) halide salts have been investigated. The diimine ligands were Ph2CN(CH2)nNCPh2 (n = 2 (Bz2en, 1a), 3 (Bz2pn, 1b), 4 (Bz2bn, 1c)), N,N′-bis-(2-tert-butylthio-1-ylmethylenebenzene)-2,2′diamino-biphenyl (2), N,N′-bis-(2-chloro-1-ylmethylenebenzene)-1,3-diaminobenzene (3) and N,N′-bis-(2-chloro-1-ylmethylenebenzene)-1,2-ethanediamine (4). Reactions of 1a-c, 2-4 with CuCl2·2H2O in dry ethanol at ambient temperature led to complete or partial hydrolysis of the diimine ligands to ultimately form copper diamine complexes. The non-hydrolyzed complexes of 1b and 1c, [Cu(L)Cl2] (L = 1b, 1c), could be isolated when the reactions were carried out at low temperatures, and the half-hydrolyzed complex [Cu(Bzpn)Cl2] could also be identified via X-ray crystallography. Similarly, reactions of 1a or 1b with NiCl2·6H2O or [NiBr2(dme)] led to rapid hydrolysis of the imines and Ni complexes containing half-hydrolyzed 1a (Bzen; [trans-[Ni(Bzen)2Br2]) and 1b (Bzpn; [Ni(Bzpn)Br2] could be isolated and identified via single crystal X-ray analysis. Kinetic studies were made of the hydrolyses of 1a, 1b in THF and 2 in acetone, in the presence of Cu(II), and of 1a in acetonitrile, in the presence of Ni(II). Activation parameters were determined for the latter reaction and for the copper-catalyzed hydrolysis of 2; the relatively large negative activation entropies clearly indicate rate-determining steps of an associative nature. 相似文献
16.
Using a racemic mixture of the tridentate ligand, (((2-pyridyl)ethylamine)methyl)phenolate ion (L−) and , NCS−, (NC)2N−, OAc− as coligands, complexes having the formula [Ni(L)(N3)] (1), [Ni(L)(NCS)]2 (2), [Ni2(L)2(OAc)(N(CN)2)]n (3) were prepared and structurally characterized. In 1, Ni(II) has a square planar geometry and phenolate oxygen is involved in dipolar ?Nδ+ interaction with electrophilic central nitrogen atom of coordinated azide ion. Complex 2 is dimeric in nature and nickel(II) is penta-coordinated. Compounds 1 and 2 exist as centrosymmetric dimers made up of a pair of R and S enantiomers of L. In 3, an acetate and phenoxo bridged dinickel complex is present which is further linked to a zig-zag coordination polymer by the dicyanamide ion. In a given chain of 3, both L have same enantiomeric form and either RR or SS dimers are repeated along the chain. The magnetic properties are described. 相似文献
17.
Kazuhiro Takenaka 《Inorganica chimica acta》2004,357(13):3895-3901
Novel upper-rim modified tetraphosphinocalix[4]arenes (5a-b) adopting 1,3-alternate conformation have been synthesized. Reaction of 5,11,17,23-tetrachloromethyl-25,26,27,28-tetrahydroxycalix[4]arene (1) with Ph2POEt gave 5,11,17,23-tetrakis(diphenylphosphinoylmethyl)-25,26,27,28-tetrahydroxycalix[4]arene (2). Tetra-O-substitution of 2 with n-propyl iodide or benzyl bromide in the presence of K2CO3 carried out to afford 5,11,17,23-tetrakis(diphenylphosphinoylmethyl)-25,26,27,28-tetrapropoxy-(3a) or -benzyloxycalix[4]arene (3b), whereas di-O-substituted calix[4]arene, 5,11,17,23-tetrakis(diphenylphosphinoylmethyl)-25,27-dipropoxy-26,28-dihydroxycalix[4]arene (4), was obtained exclusively when Na2CO3 was used as base. Reduction of 3a-b with PhSiHCl2 afforded 5,11,17,23-tetrakis(diphosphinomethyl)-25,26,27,28-tetrapropoxy-(5a) and -tetrabenzyloxycalix[4]arene (5b). 1H and 13C NMR analysis reveals that the phosphines (5a-b) and the tetra-O-substituted phosphine oxides (3a-b) adopt 1,3-alternate conformation, while the parent tetrahydroxy-(2) and the di-O-propylated phosphine oxide (4) adopt cone-conformation. The X-ray structure indicates that the calix[4]arene moieties in 4 a pinched-cone conformation in solid state. Complexation of the phosphine ligand (5a) with [RuCl2(p-cymene)]2 affords the tetranuclear complexes, [{RuCl2(p-cymene)}2 · 5a] (6), as 1,3-alternate conformer. 相似文献
18.
Bellam Sreenivasulu 《Inorganica chimica acta》2009,362(8):2735-281
Complexes [Cu(HSas)(H2O)] · 2H2O (H3Sas = N-(2-hydroxybenzyl)-l-aspartic acid) (1), [Cu(HMeSglu)(H2O)] · 2H2O (H3MeSglu = (N-(2-hydroxy-5-methylbenzyl)-l-glutamic acid) (2), [Cu2(Smet)2] (H2Smet = (N-(2-hydroxybenzyl)-l-methionine) (3), [Ni(HSas)(H2O)] (4), [Ni2(Smet)2(H2O)2] (5), and [Ni(HSapg)2] (H2Sapg = (N-(2-hydroxybenzyl)-l-aspargine) (6) have been synthesized and characterized by chemical and spectroscopic methods. Structural determination by single crystal X-ray diffraction studies revealed 1D coordination polymeric structures in 2 and 4, and hydrogen-bonded network structure in 5 and 6. In contrast to previously reported coordination compounds with similar ligands, the phenol remains protonated and bonded to the metal ions in 2 and 4, and also probably in 1. However, the phenolic group is non-bonded in 6. 相似文献
19.
Two sets of ligands, set-1 and set-2, have been prepared by mixing 1,3-diaminopentane and carbonyl compounds (2-acetylpyridine or pyridine-2-carboxaldehyde) in 1:1 and 1:2 ratios, respectively, and employed for the synthesis of complexes with Ni(II) perchlorate, Ni(II) thiocyanate and Ni(II) chloride. Ni(II) perchlorate yields the complexes having general formula [NiL2](ClO4)2(L = L1 [N3-(1-pyridin-2-yl-ethylidene)-pentane-1,3-diamine] for complex 1 or L2[N3-pyridin-2-ylmethylene-pentane-1,3-diamine] for complex 2) in which the Schiff bases are monocondensed terdentate, whereas Ni(II) thiocyanate results in the formation of tetradentate Schiff base complexes, [NiL(SCN)2] (L = L3[N,N′-bis-(1-pyridin-2-yl-ethylidine)-pentane-1,3-diamine] for complex 3 or L4 [N,N′-bis(pyridin-2-ylmethyline)-pentane-1,3-diamine] for complex 4) irrespective of the sets of ligands used. Complexes 5 {[NiL3(N3)2]} and 6 {[NiL4(N3)2]} are prepared by adding sodium azide to the methanol solution of complexes 1 and 2. Addition of Ni(II) chloride to the set-1 or set-2 ligands produces [Ni(pn)2]Cl2, 7, as the major product, where pn = 1,3-diaminopentane. Formation of the complexes has been explained by the activation of the imine bond by the counter anion and thereby favouring the hydrolysis of the Schiff base. All the complexes have been characterized by elemental analyses and spectral data. Single crystal X-ray diffraction studies confirm the structures of three representative members, 1, 4 and 7; all of them have distorted octahedral geometry around Ni(II). The bis-complex of terdentate ligands, 1, is the mer isomer, and complexes 4 and 7 possess trans geometry. 相似文献
20.
Kiyoshi Fujisawa Tomonori Kakizaki Yoshitaro Miyashita Ken-ichi Okamoto 《Inorganica chimica acta》2008,361(4):1134-1141
Five-coordinate thiolato complexes, [L1M(SMeIm)] (M = Co and Ni) (L1 = hydrotris(3,5-diisopropyl-1-pyrazolyl)borate anion and HSMeIm = 2-mercapto-1-methylimidazole), were synthesized. These complexes were compared with the corresponding Cu(II) and Zn(II) complexes with the same ligands and were also compared with the related four-coordinate complexes [L1M(SC6F5)] (HSC6F5 = pentafluorobenzenthiol). All the complexes were characterized by X-ray crystallography and UV-Vis absorption, IR, 1H NMR, and other spectroscopic techniques. All five-coordinate thiolato complexes, [L1M(SMeIm)] (M = Co, Ni, and Cu), form a distorted square pyramidal structure with a high spin state, and only [L1Zn(SMeIm)] takes a four-coordinate structure with a distorted tetrahedral configuration. The N21-M-S bond angles of the obtained five-coordinate complexes were proportional to the corresponding d value, which comes from between the equatorial basal plane with N4S ligand donor sets and metal ion. These observations and M-S bond distances affect on UV-Vis and far-IR spectral behavior. 相似文献