共查询到20条相似文献,搜索用时 15 毫秒
1.
A study of the complexation of heavy metal ions by the coronands 3,12,20,29-tetraoxa-35,36-diazapentacyclo[29.3.1.1.14,18.05,10.022,27]-hexatriaconta-1(35),5(10),6,8,14,16,18(36),22(27),23,25,31,33-dodecaene (1); 2,3,11,12-bis (4′-methylbenzo)-1,4,10,13-tetrathia-7,16-dioxacyclo-octadeca-2,11-diene (2); 7,16-diaza-1,4,10,13-tetraoxa-2,3,11,12-dibenzocyclooctadeca-2,11-diene (3); 2-[19-(2-hydroxy-2-phenylethyl)-7,8,9,10, 18,19,20,21-octahydro-6H,17H-dibenzo[b,k][1,4,10,13,7,16]tetraoxadiazacyclooctadecin-8-yl]-1-phenyl-1-ethanol (4); 1,4,10,13-tetraoxa-7,16-diazacyclo-octadecane (5); and 2-[16-(2-hydroxy-2-phenylethyl)-1,4,10,13-tetraoxa-7,16-diazacyclo-octadecanyl]-1-phenyl-1-ethanol (6) is described. Coronands 1 and 3 were prepared by literature methods, improved methods were used to prepare 2, and 4 and 6 were prepared from 3 and 5 (obtained commercially), respectively. Potentiometric studies in N,N-dimethylformamide yielded (logK/dm3 mol−1)=5.50, 6.49, 9.42 and 7.52 for [Ag · 1]+, [Ag · 2]+, [Ag · 5]+ and [Ag · 6]+, respectively; <2, <2, 4.30 and <2 for [Zn · 1]2+, [Zn · 2]2+, [Zn · 5]2+ and [Zn · 6]2+, respectively, <2, <2, 5.92 and >7.52 for [Cd · 1]2+, [Cd · 2]2+, [Cd · 5]2+, and [Cd · 6]2+, respectively, and 2.62, 2.38, 6.71 and >7.52 for [Pb · 1]2+, [Pb · 2]2+, [Pb · 5]2+, and [Pb · 6]2+, respectively. ESI-MS studies of the interactions of 1-6 with Ag+, Zn2+, Cd2+ and Pb2+ are also reported. 相似文献
2.
Norbert Kuhn Ahmed Abu-Rayyan Klaus Eichele Simon Schwarz Manfred Steimann 《Inorganica chimica acta》2004,357(6):1799-1804
The 2-bromoimidazolium bromide [ImBr]Br (5, Im=2,3-dihydro-1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) is prepared from Im (4) and bromine. From 4 and CBr4, the adduct [ImBr]Br · CBr4 (6) is obtained. 5 reacts with TeBr4 to give the salt [ImBr][TeBr5] (7). The crystal structures of 5-7 reveal the presence of weak interionic Br to Br interactions which are discussed on comparison with the structure of [ImI]I (8) and similar compounds. 相似文献
3.
The reaction of the octahedral mononuclear complex, trans(N)-[Co(l-pen-N,O,S)2]− (pen = penicillaminate), with [PtCl2(bpy)] (bpy = 2,2′-bipyridine) stereoselectively gave an optically active S-bridged dinuclear complex, [Pt(bpy){Co(l-pen)2}]Cl · 3H2O (2Cl · 3H2O), whose structure is enantiomeric to the previously reported [Pt(bpy){Co(d-pen)2}]Cl · 3H2O (1Cl · 3H2O). The mixture of equimolar amounts of 1Cl · 3H2O and 2Cl · 3H2O in H2O crystallizes as [Pt(bpy){Co(d-pen)2}]0.5[Pt(bpy){Co(l-pen)2}]0.5Cl · 7H2O (3Cl · 7H2O), in which the enantiomeric complex cations 1 and 2 are included in the ratio of 1:1. The crystal structures of 2Cl · 3H2O and 3Cl · 7H2O were determined by X-ray crystallography, and compared with that of 1Cl · 3H2O. The structural feature for 2 is essentially consistent with that for 1, except for the absolute configurations around the octahedral Co(III) center. The optically active complex cation 2 exists as a monomer, accompanied by no intermolecular interactions in the π-electronic systems of bpy moieties. In the crystals of 3Cl · 7H2O, on the other hand, the enantiomeric complex cations, [Pt(bpy){Co(d-pen)2}]+ and [Pt(bpy){Co(l-pen)2}]+, are arranged alternately while overlapping the bpy planes along a axis, and the π electronic system of the bpy framework in [Pt(bpy){Co(d-pen)2}]+ interacts with those in [Pt(bpy){Co(l-pen)2}]+. Differences between the crystal structures of 2Cl · 3H2O and3Cl · 7H2O significantly reflect their diffuse reflectance spectra. In aqueous solution, each cation in both 2Cl · 3H2O and 3Cl · 7H2O is comparatively put on a free environment without such intermolecular interactions. 相似文献
4.
Qian Huang Li-Bo Liang Hong-Rong Zuo Le-Min Yang Xue-Lei Hu 《Inorganica chimica acta》2010,363(11):2546-2552
Three new ion-pair complexes, [4RBzDMAP]2[Cu(mnt)2] (mnt2− = maleonitriledithiolate; [4RBzDMAP]+ = 1-(4′-R-benzyl)-4-dimethylaminopyridinium, R = F(1), Cl(2) and Br(3)) were synthesized and characterized by elemental analyses, IR, UV, single crystal X-ray diffraction and magnetic measurements. The [Cu(mnt)2]2− anions and the cations stack alternately and form a 1D column via C-H···S, C-H···π or C-H···Cu interactions for 1 and 2. While the cations stack into a column though π···π or C-H···π interactions between pyridine and phenyl rings for 1 and 3. The change of the molecular topology of the counteraction when the 4-substituted group in the benzyl ring have been changed from F or Cl to Br atom, results in the difference in the crystal system, space group and the stacking mode of the cations and anions of 1, 2 and 3. Some weak hydrogen bonds between the adjacent columns further generate a 3D network structure. It is interesting that 1 and 2 exhibits antiferromagnetic coupling with θ = −2.372 K and θ = −14.732 K, while 3 shows weak ferromagnetic coupling feature with θ = 0.381 K. 相似文献
5.
Ashish Kumar Singh Sanjay Kumar Singh Daya Shankar Pandey 《Inorganica chimica acta》2010,363(5):995-1000
Synthesis of complexes with the formulations [M(CPI)2Cl2] (M = Zn, 1; M = Cd, 4) and [M(CPI)6](X)2 (M = Zn, X = NO3−, 2; X = ClO4−, 3; M = Cd, X = NO3−, 5; X = ClO4−, 6) have been achieved from the reactions of MCl2, M(NO3)2·xH2O and M(ClO4)2·xH2O (M = Zn, Cd) with 1-(4-cyanophenyl)-imidazole (CPI). Complexes 1-6 have been characterized by elemental analyses and spectral studies (IR, 1H, 13C NMR, electronic absorption and emission). Molecular structures of 1, 2, 3 and 6 have been determined crystallographically. Weak interaction studies on the complexes revealed presence of various interesting motifs resulting from C-H···N, C-H···Cl and π-π stacking interactions. The complexes under study exhibit strong luminescence at ∼450 nm in DMSO at room temperature. 相似文献
6.
Ngai-Man Lam Chun-Sing Lai Qian-Feng Zhang Wa-Hung Leung 《Inorganica chimica acta》2009,362(15):5190-5194
Treatment of [Bun4N][Ru(N)Cl4] with Na(OR) afforded [Bun4N][Ru(N)(OR)4] (R = C6F5 (1), C6F4H (2), C6Br5 (3)), whereas that with [Bun4N][Os(N)Cl4] gave [Bun4N][Os(N)(OR)3Cl] (R = C6F5 (4), C6F4H (5), C6Br5 (6)). Treatment of [Bun4N][M(N)Cl4] with Na(SC6F4H) and Na(Sxyl) (xyl = 2,6-dimethylphenyl) afforded [Bun4N][M(N)(SC6F4H)4] (M = Ru (7), Os (8)) and [Bun4N][M(N)(Sxyl)4] (M = Ru (9), Os (10)), respectively. The crystal structures of compounds 1, 6 and 9 have been determined. 相似文献
7.
Two oxime-functionalized diazamesocyclic derivates, namely, N,N′-bis(acetophenoneoxime)-1,4-diazacycloheptane (H2L1) and N,N′-bis(acetophenonoxime)-1,5-diazacyclooctane (H2L2), have been prepared and characterized. Both ligands (obtained in the hydrochloride form) can form stable metal complexes with CuII and NiII salts, the crystal structures of which were determined by X-ray diffraction technique. The reactions of H2L1 with Cu(ClO4)2 and Ni(ClO4)2 afford a penta-coordinated mononuclear complex [Cu(H2L1)Cl] · ClO4 (1) and a four-coordinated monomeric [Ni(HL1)] · ClO4 (2), in which the ligand is monodeprotonated. The ligand H2L2 also forms a quite similar mononuclear [Ni(HL2)] · ClO4 complex with Ni(ClO4)2, according to our previous work. However, reactions of different CuII salts [Cu(ClO4)2, CuCl2 and Cu(NO3)2 for 3, and CuSO4 for 4] with H2L2 in the presence of NaClO4 yield two unusual mono-μ-Cl dinuclear CuII complexes [Cu2(HL2)2Cl] · (ClO4) (3), and [Cu2(H2L2)(HL2)Cl] · (ClO4)2 · (H2O)(4). These results indicate that the resultant CuII complexes (1, 3 and 4) are sensitive to the backbones of diazamesocycles and even auxiliary anions. 相似文献
8.
Qing-Xiang Liu Hui-Long Li Xiao-Jun Zhao Shu-Sheng Ge Meng-Chao Shi Gang Shen Yan Zang Xiu-Guang Wang 《Inorganica chimica acta》2011,376(1):437-445
A series of NHC silver(I), mercury(II) and palladium(II) complexes, [(1,3-diethylbimy)6Ag4I3]I (2), [(1-benzyl-3-picolylbimy)Ag2Br2]n (3), [(1-benzyl-3-picolylbimy)HgI(CH2CN)]2 (4), {[(1-picolyl-3-npropylbimy)2Hg][Hg2I6]}n (5) and [(1,3-dipicolylbimy)PdCl]Cl (6), as well as one anionic complex [1,3-diethylbimidazolium]2[HgI4] (1) (bimy = benzimidazol-2-ylidene), have been prepared and characterized. Interestingly, a wind wheel-like Ag4I3 arrangement in 2 is formed, 1D polymeric chain containing 12-membered macrometallocycles and quadrangle Ag2Br2 units in 3 is generated, and the α-carbon atom of deprotonated acetonitrile ([CH2CN]−) in 4 participates in coordination with mercury(II) atom. In the crystal packings of complexes 1-6, 2D supramolecular layers or 3D supramolecular architectures are formed via intermolecular weak interactions, including π-π interactions, hydrogen bonds, C-H···π contacts, weak Hg···I bonds and I···I bonds. Additionally, the catalytic activity of the NHC palladium(II) complex 6 in Suzuki-Miyaura cross-coupling reaction was studied. 相似文献
9.
The manganese complexes [MnII(Hbmimpm)2(NO3)](NO3) · Et2O (1), [MnIII(bmimpm)2(OAc)] · 2CH2Cl2(2), and [MnIII(bmiapm)2(OAc)] · MeOH · H2O · CH2Cl2(3) containing the new ligands Bis(1-methylimidazol-2-yl)-(4-methoxyphen-1-yl)methanol (Hbmimpm) and Bis[(1-methylimidazol-2-yl)](2-aminophenyl)methanol (Hbmiapm) were synthesized. They are good structural models for the reduced (1) and oxidized (2, 3) form of manganese superoxide dismutase. All complexes were characterized by spectroscopic methods and X-ray structure analysis. Compounds 1 and 2 crystallize in the monoclinic space group P21/c whereas complex 3 crystallizes in the monoclinic space group P21/n. The coordination sphere around the manganese cores is distorted octahedral with two corresponding tridentate ligands representing the protein ligands and one nitrate (1) or acetate (2, 3) ion occupying two cis positions. Similar to the enzyme the Mn(III) complex 2 reacts with sodium azide. The obtained microcrystalline azide adduct was characterized by UV-Vis and IR spectroscopy. 相似文献
10.
Lei Gou Zhong-Xi Han Qing-Ran Wu Zhen-Hua Yang Fei Wang Gang-Lin Xue 《Inorganica chimica acta》2010,363(11):2590-2599
Five structurally diverse complexes, [Cd2(pyip)2(suc)2]n·1.5nH2O (1), [Zn(pyip)(glu)]n (2), [Cd(pyip)(glu)]n (3), [Zn(pyip)2(adip)2]n·2.5nH2O (4), [Cd3(pyip)2(adip)3]n (5) (pyip = 2-(pyridin-3-yl)-1H-imidazo[4,5-f][1,10]phenan-throline, H2suc = succinic acid, H2glu = glutaric acid, H2adip = adipic acid), have been hydrothermally synthesized. Complexes 1 and 4 are ribbon-like chains, in which pyip ligands attach to the both sides of the chain in pairs. Complex 2 is a one dimensional (1D) wave-like chain, while the pyip ligands attach to only one side of the chain. Complexes 3 and 5 are both two dimensional (2D) networks, in which the dicarboxylate ligands connect the dinuclear or trinuclear CdII units into layers with (4, 4) topological network. The structural differences among these complexes show that the organic acids have important influences on the final structures. 相似文献
11.
Qian Huang Jun Tian Jia-Rong Zhou Chun-Lin Ni Xue-Lei Hu 《Inorganica chimica acta》2009,362(10):3569-424
Syntheses, structural characterizations, magnetic behaviors and theoretical analyses of two new ion-pair complexes, [IFBzIQl][Ni(mnt)2](1) and [IClBzIQl]2[Ni(mnt)2]2 · MeCN(2) [IFBzIQl][Ni(mnt)2] ([IFBzIQl]+ = 1-(2′-fluoro-4′-iodobenzyl)isoquinolinium, [IClBzIQl]+ = 1-(2′-chloro-4′-iodobenzyl)isoquinolinium, mnt2− = maleonitriledithiolate), have been investigated. In crystal of 1, the [Ni(mnt)2]− anions and the [IFBzIQl]+ cations stack into an alternating column through π?π stacking interactions. The anions of both 1 and 2 form a dimer via π?π stacking and S?S short interactions between the [Ni(mnt)2]− anions. The overlapping mode of two neighboring [Ni(mnt)2]− anions in the dimer is the Ni-ring fashion with a Ni?Ni distance of 4.076 Å for 1, and ring-ring fashion with the Ni?Ni and S?S distances being 4.395 and 3.593 Å for 2. Some weak interactions such as π?π, C?N, C-H?F or C-H?N in 1 and 2 play a crucial role in stacking and stabilizing the crystal lattice, and give a 3D network structure and exchange pathways of the magnetic interaction for 1 and 2. Magnetic susceptibility measurements for 1 and 2 in the temperature range 1.8-300 K show that the overall magnetic behavior indicates the presence of antiferromagnetic interaction, while 2 exhibits an activated magnetic behavior in the high-temperature region (HT) together with a Curie tail in the low-temperature region (LT). 相似文献
12.
In order to further understand the coordination chemistry of diazamesocyclic systems, a series of mononuclear NiII complexes with 1,4-diazacycloheptane (DACH) functionalized by additional imidazole or pyridine donor pendants, including [NiL1](ClO4)2 · H2O (1), [NiL1Cl](ClO4) (2), [NiL2Cl](ClO4) · CH3OH (3), [NiL2Cl][NiL2](ClO4)3 (4) and [NiL3](ClO4)2 (5), where L1 = 1,4-bis(N-1-methylimidazol-2-yl-methyl)-1,4-diazacycloheptane, L2 = 1,4-bis(pyridyl-2-yl-methyl)-1,4-diazacycloheptane, and L3 = 1,4-bis-(imidazol-4-yl-methyl)-1,4-diazacycloheptane, have been prepared and characterized. A detailed study on the solid structures and solution spectra of these complexes indicates that tetradentate ligands L1, L2 and L3 would lead to new NiII complexes with different coordination environments in the solid states and solution. The N-methyl substituted imidazole functionalized ligand L1 forms green compound 2 and yellow product 1; while the pyridine functionalized ligand L2 affords red product 4 and green complex 3; the ligand L3 results in only one stable mononuclear NiII product 5. The solution behaviors of these interesting compounds were also investigated by UV-Vis technique. 相似文献
13.
Shu Qin Liu Takayoshi Kuroda-Sowa Hisashige Ito Megumu Munakata 《Inorganica chimica acta》2004,357(12):3621-3631
Four copper(I) complexes of 2,11-dithia[3.3]paracyclophane (dtpcp), [CuI(dtpcp)] · MeCN (1), [CuBr(dtpcp)] · MeCN (2), [CuCl(dtpcp)] · MeCN (3) and [Cu2I2(dtpcp)2] · Me-thf (4) (Me-thf=2-methyltetrahydrofuran), have been synthesized and their molecular structures determined by X-ray crystallography. Complexes 1 and 2 are isostructural, and exhibit 3D networks with elliptical channels along a-axis, which are constructed by dtpcp molecules bridging zigzag CuI and CuBr chains, respectively. Complexes 3 and 4 are 2D porous sheet networks constructed by bridging the zigzag copper-dtpcp chains via rhombic ring of Cu2X2 (X=Cl or I). All sheets in 3 are packed in an eclipsed manner through π-π stackings to generate channels along the a-axis. However, the 2D porous sheets in 4 are packed in an offset mode such that channels are not formed along c-axis. Complexes 1 and 2 can reversibly incorporate guest acetonitriles without collapse of structures, and the original frameworks of 1 and 2 are completely recovered after incorporation of guests which are confirmed by X-ray powder diffraction (XRPD) pattern and 1H NMR spectrum. Additionally, complex 1 exhibits selectivity in size and polarity for guest inclusion. 相似文献
14.
Two new mononuclear spin-crossover iron(II) complexes, [FeL2(NCS)2] · H2O (1) and [FeL2(NCSe)2] (2), have been synthesized from the reaction of the versatile ligand 4,5-bis(2-cyanoethylthio)-2-bis(2-pyridyl)methylene-1,3-dithiole (L), Fe(ClO4)2, and KNCX (X = S/Se). Reactions of L with CuII or CoII salts afford one mononuclear complex [CuL(hfac)2] · CH3OH (hfac = hexafluoroacetylacetonate) (3), one dinuclear complex [(CuLCl)2(μ-Cl)2] · CH3OH (4), and two 1D chain species, [CuL2]n(BF4)2n (5) and [CoL2]n(ClO4)2n · 2nCH2Cl2 (6). The crystal structures of complexes 1 and 3-6 have been determined by X-ray crystallography. Short intermolecular S?S contacts between neighboring 1D arrays are observed in 5 and 6, which lead to the formation of the 2D structure. The magnetic properties are studied, and antiferromagnetic couplings between the CuII centers across the chloride bridges have been found in 4 (J = 2.04 cm-1). Spin-crossover behaviors between high and low spin states are observed at T1/2 = 80 K for 1 and T1/2 = 300 K for 2, respectively. 相似文献
15.
The reaction of trans(N)-[Co(d-pen)2]− (pen = penicillaminate) with HgCl2 or HgBr2 in the molar ratios of 1:1 gave the sulfur-bridged heterodinuclear complex, [HgX(OH2){Co(d-pen)2}] (X = Cl (1a) or Br (1b)). A similar reaction in the ratio of 2:1 produced the trinuclear complex, [Hg{Co(d-pen)2}2] (1c). The enantiomers of 1a and 1c, [HgCl(OH2){Co(l-pen)2}] (1a′) and [Hg{Co(l-pen)2}2] (1c′), were also obtained by using trans(N)-[Co(l-pen)2]− instead of trans(N)-[Co(d-pen)2]−. Further, the reaction of cis · cis · cis-[Co(d-pen)(l-pen)]− with HgCl2 in the molar ratio of 1:1 resulted in the formation of [HgCl(OH2){Co(d-pen)(l-pen)}] (2a). During the formations of the above six complexes, 1a, 1b, 1c, 1a′, 1c′, and 2a, the octahedral Co(III) units retain their configurations. On the other hand, the reaction of cis · cis · cis-[Co(d-pen)(l-pen)]− with HgCl2 in the molar ratio of 2:1 gave not [Hg{Co(d-pen)(l-pen}2] but [Hg{Co(d-pen)2}{Co(l-pen)2}] (2c), accompanied by the ligand-exchange on the terminal Co(III) units. The X-ray crystal structural analyses show that the central Hg(II) atom in 1c takes a considerably distorted tetrahedral geometry, whereas that in 2c is of an ideal tetrahedron. The interconversion between the complexes is also examined. The electronic absorption, CD, and NMR spectral behavior of the complexes is discussed in relation to the crystal structures of 1c and 2c. 相似文献
16.
Maurizio Lanfranchi Clara Mora Maria Angela Pellinghelli 《Inorganica chimica acta》2004,357(2):367-375
The ligand hydrotris(1,4-dihydro-3-methyl-4-phenyl-5-thioxo-1,2,4-triazolyl)borato (TrPh,Me) was synthetized as natrium salt and the complexes [Zn(TrPh,Me)2] · 7.5H2O · 1.5CH3CN (2a), [Zn(TrPh,Me)2] · 8DMF (2b), [Co(TrPh,Me)2] · 8DMF (3a), [Ni(TrPh,Me)2] · H2O · 6DMSO (4a), [Bi(TrPh,Me)2]NO3 (5), have been isolated and structurally characterized by X-ray diffraction. In the zinc derivatives the ligand adopts different denticity and coordination modes, η2 and [S2] for 2a and η3 and [N3] for 2b, depending on the crystallization solvent, giving rise to tetrahedral and octahedral geometry, respectively. In the octahedral cobalt and nickel complexes the ligand is η3 and [N3] coordinated whereas in the bismuth complex the η3 and [S3] coordination is exhibited. 相似文献
17.
Salah S. Massoud Franz A. Mautner Febee R. Louka Sebastian Dechert 《Inorganica chimica acta》2011,370(1):435-443
The reaction of aqueous solutions of the preformed 1:1 Cu(ClO4)2-polydentate amine with tetrasodium 1,2,4,5-benzene tetracarboxylate (Na4bta) afforded three different types of polynuclear compounds. These include the tetranuclear complexes: [Cu4(Medpt)4(μ4-bta)(ClO4)2(H2O)2](ClO4)2·2H2O (1), [Cu4(pmdien)4(μ4-bta)(H2O)4](ClO4)4 (2), [Cu4(Mepea)4(μ4-bta)(H2O)2](ClO4)4(3), [Cu4(TPA)4(μ4-bta)](ClO4)4·10H2O (4) and [Cu4(tepa)4(μ4-bta)](ClO4)4·2H2O (5), the di-nuclear: [Cu2(DPA)2(μ2-bta)(H2O)2]·4H2O (6), [Cu2(dppa)2(μ2-bta)(H2O)2]·4H2O (7) and [Cu2(pmea)2(μ2-bta)]·14H2O (8) and the trinuclear complex [Cu3(dppa)3(μ3-bta)(H2O)2.25](ClO4)2·6.5H2O (9) where Medpt = 3,3′-diamino-N-methyldipropylamine, pmedien = N,N,N′,N″,N″-pentamethyldiethylenetriamine, Mepea = [2-(2-pyridyl)ethyl]-(2-pyridylmethyl)methylamine, TPA = tris(2-pyridylmethyl)amine, tepa = tris[2-(2-pyridyl)ethyl)]amine, DPA = di(2-pyridymethyl)amine, dppa = N-propanamide-bis(2-pyridylmethyl)amine and pmea = bis(2-pyridylmethyl)-[2-(2-pyridylethyl)]amine. The complexes were structurally characterized by elemental analyses, spectroscopic techniques, and by X-ray crystallography for complexes 1, 2, 4, 6, 7 and 9. X-ray structure of the complexes reveal that bta4− is acting as a bridging ligand via its four deprotonated caboxylate groups in 1, 2 and 4, three carboxylate groups in 9 and via two trans-carboxylates in 6 and 7. The complexes exhibit extended supramolecular networks with different dimensionality: 1-D in 2 and 4 due to hydrogen bonds of the type O-H···O, 2-D in 1 and 7, and 3-D network in 6 as a result of hydrogen bonds of the types N-H···O and O-H···O. Magnetic susceptibility measurements showed very weak antiferromagnetic coupling between the CuII ions in 1-5, 7-9 (|J| = 0.02-0.87 cm−1) and weak ferromagnetic coupling for 6 (J = 0.08 cm−1). 相似文献
18.
Arpita Jana Malabika Nayak Supriya Dutta Sasankasekhar Mohanta 《Inorganica chimica acta》2011,365(1):71-214
Reaction of [CuIIL⊂(H2O)] (H2L = N,N′-ethylenebis(3-ethoxysalicylaldimine)) with nickel(II) perchlorate in 1:1 ratio in acetone produces the trinuclear compound [(CuIIL)2NiII(H2O)2](ClO4)2 (1). On the other hand, on changing the solvent from acetone to methanol, reaction of the same reactants in same ratio produces the pentametallic compound [(CuIIL)2NiII(H2O)2](ClO4)2·2[CuIIL⊂(H2O)]·2MeOH (2A), which loses solvated methanol molecules immediately after its isolation to form [(CuIIL)2NiII(H2O)2](ClO4)2·2[CuIIL⊂(H2O)] (2B). Clearly, formation of 1 versus 2A and 2B is solvent dependent. Crystal structures of 1 and 2A have been determined. Interestingly, compound 2A is a [3 × 1 + 1 × 2] cocrystal. The cryomagnetic profiles of 1 and 2B indicate that the two pairs of copper(II)···nickel(II) ions in the trinuclear cores in both the complexes are coupled by almost identical moderate antiferromagnetic interaction (J = −22.8 cm−1 for 1 and −26.0 cm−1 for 2B). 相似文献
19.
The reaction of [PtMe3(MeOH)(bpy)][BF4] (1) with the thionucleobases 2-thiocytosine (SCy, 2) and 1-methyl-2-thiocytosine (1-MeSCy, 3) resulted in the formation of the complexes [PtMe3(bpy)(SCy-κS)][BF4] (4) and [PtMe3(bpy)(1-MeSCy-κS)] [BF4] (5), respectively. The complexes were characterized by 1H and 13C NMR spectroscopy as well as by single-crystal X-ray analyses of 4 · MeOH and 5. In 4 · MeOH two strong hydrogen bonds (N4-H?N3′: N4?N3′ 2.976(7) Å) between the thiocytosine ligands give rise to base pairing thus forming dinuclear cations [{PtMe3(bpy)(SCy-κS)}2]2+. In both complexes the platinum atom is octahedrally coordinated [PtC3N2S] by three methyl ligands, the 2,2′-bipyridine ligand and the κS coordinated nucleobase (configuration index: OC-6-33). The structural investigations gave evidence that the sulfur atoms of the nucleobase ligands in 4 · MeOH and 5 have to be regarded as sp3 and sp2 hybridized, respectively. Thus, the ligand in 4 · MeOH has to be considered as the deprotonated thiol-amino form of thiocytosine being reprotonated at N1. In complex 5 the 1-MeSCy is coordinated in its thione-amino form. DFT-calculations of the base-paired dinuclear cation in 4 as well as of 4 itself gave proof of the strength of the hydrogen bond (8.5 kcal/mol) and exhibited that cation-anion interactions influence the conformation of the complex. In vitro cytotoxicity studies of 4 and 5 using nine different human tumor cell lines revealed moderate cytotoxic activity. 相似文献
20.
H. Hanika-Heidl 《Inorganica chimica acta》2004,357(6):1748-1760
Single crystals of three derivatives of the structurally still incompletely characterized coordination polymer [(Me3Sn)4Ru(CN)6] 1b have been prepared and subjected to crystallographic studies: [1b · 4H2O]=2b forms stacks of puckered ∞2[Ru{μ-CNSn(Me3)NC}2] sheets interlinked by hydrogen bonds in making use of two additional CNSn(Me3)OH2 ligands and quasi-zeolitic water. Mild drying of 2b leads to the “missing link” between 1b and 2b, [1b · 2H2O], 3b. The structure of [1b · 2tp] (tp=4-thiopyridone) consists of a three-dimensional, negatively charged host framework comprising (via Sn-S bonds) one “aromatic” thione linkage and a [Me3Sn · tp]+guest ion involving a more zwitterionic form of tp. Slow uptake of Me3SnCl from the gas phase by an aqueous solution of K4[Ru(CN)6] and tp afforded the novel assembly [1b · 2H2O · 0.8pms · 0.2pds] (pms/pds=4,4′-dipyridylmono-/disulfide), the supramolecular architecture of which resembles that of 2b. Bridging pms or pds molecules occupy equivalent interlayer sites, and the pms/pds ratio is likely to vary. At least three further assemblies containing again 1b and either tp or pds/pms have likewise been isolated, however, not as single crystals. 相似文献