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1.
In this study three new dinuclear Cu(II) compounds with the ligand 7-azaindole (abbreviated as Haza) and bridging end-on azide anions with the general formula [Cu2(Haza)4(N3)2(A)2] (in which A =  (1), (2) and (3)) are reported, as well as a dinuclear-based polymeric compound with the overall formula [Cu4(L)6(N3)6(ClO4)2]n·(CH3OH)2n (4). The latter compound contains both end-on and end-to-end azide anions. Full characterization of all four compounds has been performed by spectroscopic methods and by using 3D X-ray structure analysis.  相似文献   

2.
The preparation, crystal structure and variable temperature-magnetic investigation of three 2-(2′-pyridyl)imidazole-containing chromium(III) complexes of formula PPh4[Cr(pyim)(C2O4)2]·H2O (1), AsPh4[Cr(pyim)(C2O4)2]·H2O (2) and [Cr2(pyim)2(C2O4)2(OH2)2]·2pyim · 6H2O (3) [pyim = 2-(2′-pyridyl)imidazole, , and ] are reported herein. The isomorphous compounds are made up of discrete [Cr(pyim)(C2O4)2] anions, cations [X = P (1) and As (2)] and uncoordinated water molecules. The chromium environment in 1 and 2 is distorted octahedral with Cr-N and Cr-O bond distances varying in the ranges 2.040(3)-2.101(3) and 1.941(3)-1.959(3) Å, respectively. The angle subtended by the chromium(III) ion by the two didentate oxalate ligands cover the range 82.49(12)-82.95(12)°, values which are somewhat greater than those concerning the chelating pyim molecule [77.94(13) (1) and 78.50(13)° (2)]. Complex 3 contains discrete centrosymmetric [Cr2(pyim)2(C2O4)2(OH)2] neutral units where the two chromium(III) ions are joined by a di-μ-hydroxo bridge, the oxalate and pyim groups acting as peripheral didentate ligands. Uncoordinated water and pyim molecules are also present in 3 and they contribute to the stabilization of its structure by extensive hydrogen bonding and π-π type interactions. The values of the intramolecular chromium-chromium separation and angle at the hydroxo bridge in 3 are 2.9908(12) Å and 99.60(16)°, respectively. Magnetic susceptibility measurements of 1-3 in the temperature range 1.9-300 K show the occurrence of weak inter- (1 and 2) and intramolecular (3) antiferromagnetic couplings. The magnetic properties of 3 have been interpreted in terms of a temperature-dependent exchange integral, small changes of the angle at the hydroxo bridge upon cooling being most likely responsible for this peculiar magnetic behavior.  相似文献   

3.
Treatment of TeCl4 with either K[{N(C6H3Pri2-2,6)C(H)}2CPh] [≡K(L)] (1) in thf/Et2O or [H2(L)]Cl (2) in Et2O furnished [Cl4Cl?HH?OEt2]·0.5(Et2O) (3), whilst 2TeCl4 with a mixture of single equivalent portions of 2,6-Pri2C6H3NH2 and H(L) produced [Cl4] (4). The X-ray structures of each of crystalline 3 and 4 show that the Te atom is at the centre of an only slightly distorted square pyramid, with a Cl atom of 3 or a C of 4 in the axial position. The N1 and N2 atoms of the π-delocalised β-dialdiminium moiety of 3 have H-bond contacts, involving short N1-H?OEt2 and N2-H?Cl5 distances. The two longer of the four Te-Cl bonds of 4 are close to the N atom of the neighbouring molecule; whilst two of the H atoms of each H3 fragment are H-bonded to the O atoms of the two thf ligands, the third being close to two Cl atoms of an adjacent molecule, thus forming H-bonded chains of molecules.  相似文献   

4.
Two six-coordinated manganese(II) complexes [Mn(pydien)Cl](ClO4) · C2H5OH (1), [Mn(pydien)NCS](ClO4) (2) and two seven-coordinated manganese(II) complexes [Mn(pydado)Cl](ClO4) (3), [Mn(pydado)NCS](ClO4) (4) have been obtained using linear penta and hexadentate ligands pydien and pydado (pydien: 1,7-bis(2-pyridylmethyl)-1,4,7-triazaheptane and pydado: 1,10-bis(pyridylmethyl)-1,10-diaza-4,7-dioxadecane). The crystal structures for all compounds have been determined. 1 and 3 crystallize in the triclinic space group , 2 crystallizes in the orthorhombic space group Pbca, whereas 4 crystallizes in the monoclinic space group P21/c. The bound anion (chloro or isothiocyanato) in complexes 1 and 2 has no influence on the geometry of six-coordinate manganese(II) complexes, whereas the geometry and the wrapping of the hexadentate ligand (pydado) around Mn2+ cation depend on the nature of the bound anion. The complex 3 has a capped octahedron geometry with the two pyridyl groups in trans position, while the geometry of complex 4 can be described as pentagonal bipyramid with one pyridyl group and a thiocyanate anion in the axial positions.  相似文献   

5.
Tellurated alkylamine derivatives , , and have been synthesized by reacting appropriate organic halides with the nucleophile 4-CH3OC6H4Te or Te2− generated in situ by borohydride reduction of (4-CH3OC6H4Te)2 or Te powder followed by reaction with HCl of appropriate concentration. The zwitterionic species was generated when single crystals of 2 were grown in methanol at 0 °C. Complexes 1-4 exhibit characteristic 1H NMR spectra. The single crystal structures of 1-4 and 2a have been determined. In the crystals of 1, C-H?π distances have been found to be 3.31(7)-3.59(5) Å. In both 2 and 2a, weak Te?Cl interactions (3.54(2) -3.62(2) Å) are observed. The C-H?π distance in the crystal of 2 is 3.19(0) Å. In 2a and 3, water hydrogen bonds connect the water molecules with the end groups from different molecules. In the case of 3, Te?Cl weak interactions involving the Cl ions connect together two such chains. The geometry of Te in 1 is V shaped. In 2 and 3 it is pseudo trigonal bipyramidal, and in 2a, it is square pyramidal. However, in the latter case it becomes distorted octahedral due to weak Te?Cl secondary interactions. The geometry about Te in 4 is distorted octahedral due to weak Te?Cl interactions involving Cl ions. However, there are no intermolecular Te?Cl interactions.  相似文献   

6.
Reaction of 4-amino-6-methyl-1,2,4-triazin-thione-5-one (AMTTO, 1) with 2-thiophenecarboxaldehyde and 2-furaldehyde led to the corresponding iminic compounds 6-methyl-4-[thiophene-2-yl-methylene-amino]-3-thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one (TAMTTO, 2) and 4-[furan-2-yl-methylene-amino]-6-methyl-3-thioxo-[1,2,4]-triazin-3,4-dihydro(2H)-5-one (FAMTTO, 3). Treatment of 2 with AgNO3 gave the complex [Ag2(TAMMTO)4](NO3)2 · 4MeOH (4) and of 2 and 3 with [Ag(PPh3)2]NO3 gave the complexes [Ag(TAMTTO)(PPh3)2]NO3 · 1.5THF (5) and [Ag(FAMTTO)(PPh3)2]NO3 (6), respectively. All the compounds have been characterized by elemental analyses, IR spectroscopy and mass spectrometry. Compound 2 and all the complexes have been characterized by X-ray diffraction studies, respectively. In addition, 5 and 6 have been characterized by 31P NMR spectroscopy. Crystal data for 2 at −80 °C: monoclinic, space group C2/c, a=2319.6(2), b=609.8(1), c=1673.6(2) pm, β=106.14(1)°, Z=8, R1=0.0523; for 4 at −80 °C: triclinic, space group , a=877.6(1), b=1085.2(1), c=1557.7(2) pm, α=77.14(1)°, β=80.87(1)°, γ=78.18(1)°, Z=1, R1=0.0407; for 5 at 20 °C: triclinic, space group , a=1151.1(2), b=1225.1(2), c=1887.4(3) pm, α=78.04(1)°, β=86.20(1)°, γ=76.03(1)°, Z=2, R1=0.0662; for 6 at −80 °C: triclinic, space group , a=1189.7(2), b=1387.8(2), c=1410.9(2) pm, α=94.74(2)°, β=95.12(2)°, γ=112.41(2)°, Z=2, R1=0.0511.  相似文献   

7.
Assemblies of an angular dipyridyl ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo) with a series of metal perchlorate afford five new supramolecular complexes with the general formula of [M(4-bpo)2(H2O)4] · (4-bpo)2 · (anion) · (solvent), in which M = MnII for 1, FeII for 2, CoII for 3, ZnII for 4, and FeIII for 5. Although similar molecular structures and compositions are found for these mononuclear complexes, they display two types of supramolecular lattices. Complexes 1, 4 and 5 similarly crystallize in space group P2/n or P2/c. The complex cations, free 4-bpo and lattice water are linked to generate 2D layered frameworks with the aid of hydrogen bonding, and the counter anions are located within and between (also methanol in 5) these 2D arrays. However, complexes 2 and 3 are isostructural in space group . Two types of alternate 2D layers consisting of complex cations and free 4-bpo components, respectively, are observed with the anions and lattice water locating between them. These motifs are interlinked by complicated hydrogen-bonding to form a 3D intercalated network. Moreover, when Co(NO3)2 is used instead of Co(ClO4)2 in the assembly of 3, a 1D polymeric chain complex {[Co(4-bpo)(H2O)2(NO3)2](H2O)3}n (6) is generated. These results indicate that the choice of metal ion and anion exerts a significant influence on governing the target complexes. A comparison of the structural features for all metal perchlorate complexes with 4-bpo is also briefly discussed.  相似文献   

8.
The chloro complexes [PtCl2(RSR′)2] (1-10) (RSR′ = MeSCH2C(O)OMe, 1; MeSCH2C(O)OEt, 2; MeSCH2C(O)Omenthyl(−), 3; MeSCH2CH2C(O)OMe, 4; , 5; EtSCH2C(O)Me, 6; MeSCH(Me)C(O)Me, 7; MeSPh, 8; MeS-o-C6H4Me, 9; and MeS-o-C6H4Et, 10) are obtained in high yield (63-90%) by reaction of [PtCl2(PhCN)2] with the proper thioether in 1/2 molar ratio, in anhydrous chloroform, at reflux under argon for ca. 10 h. The X-ray crystal structure of [PtCl2(MeS-o-C6H4Me)2] (9) shows an almost regular trans square planar geometry (triclinic, space group , a 6.806(1), b 7.789(2), c 10.085(3) Å, α 101.80(2)°, β 69.55(2)°, γ 115.27(2)°, R(Fo) 0.023, ). The dichloro complexes react with silver acetate in a complex manner, which depends on the nature of the thioether, and only with RSR′ = MeSPh the simple diacetato complex [Pt(OAc)2(RSR′)2] is obtained as the major product.  相似文献   

9.
(where mnt = 1,2-dicyanoethylenedithiolate) (1), reacts with HX (X = SPh, Cl, Br) to form a series of complexes, . In acidic-alcoholic medium 1 with thiophenol yields another series of compounds, . Under similar conditions tertiary-butanol does not coordinate where a complex can only be isolated in the presence of bromide as . The use of excess of methanesulfonic acid in the presence of HSPh or HSEt facilitates methanesulfonate coordination in complexes, . All these complexes are structurally characterized by single crystal X-ray study. These complexes show pH dependent hydrolytic reaction leading to quantitative reversal to the starting complex, 1. Complexes 2a-c respond to hydrolysis in CH2Cl2 with the intermediate formation of EPR active molybdenum(V) species.  相似文献   

10.
Reaction of [Tp′W(CO)2(PhCCPh)][OTf] (1b) (Tp′ = hydridotris(3,5-dimethylpyrazolyl)borate) with excess aziridine or 2-methylaziridine followed by protonation with produces chiral tungsten(II) amine complexes (3, 4; R = Me, Ph). An azetidine amido complex, Tp′W(CO)(PhCCMe)(H2) (5) is synthesized by reaction of [Tp′W(CO)2(PhCCMe)][OTf] (1a) with excess azetidine. Oxidation of amido complex 5 with I2 in the presence of a weak base provides the corresponding 1-azetine complex, (6). Addition of methylmagnesium bromide to complex 6 results in formation of predominantly one diastereomer (SWRC/RWSC) (96:4 dr) of the 2-methylazetidine complex, Tp′W(CO)(PhCCMe)(H2) (7). Reaction of complex 5 with results in formation of a cationic azetidine complex, (8). Reaction of 1b with excess piperidine followed by oxidation affords 2,3,4,5-tetrahydropyridine complex 9b, . Formation of an enamido complex, Tp′W(CO)(PhCCPh)(H2) (10), is observed upon addition of base to 9b. Subsequent addition of [D+] to the enamido β-carbon results in the formation of the deuterated product, 9b-d1, as determined by 2H NMR. Seven X-ray crystal structures have been determined, and these encompass complexes with 3, 4, and 6-membered heterocyclic ligands. Crystal structures are reported for two aziridine adducts (2, 4) two neutral amido complexes (5, 7), one cationic imine complex (6), and one cationic amine (8) complex derived from azetidine, and the imine complex formed from piperidine (9).  相似文献   

11.
A new series of dinuclear squarato-bridged nickel(II) and copper(II) complexes [Ni2(2,3,2-tet)21,3-C4O4)(H2O)2](ClO4)2 (1), [Ni2(aepn)21,3-C4O4)(H2O)2](ClO4)2 (2), [Cu2(pmedien)21,3-C4O4)(H2O)2](ClO4)2.4H2O (3) and [Cu2(DPA)21,2-C4O4)(H2O)2](ClO4)2 (4) where is the dianion of 3,4-dihydroxycyclobut-3-en-1,2-dione (squaric acid), 2,3,2-tet = 1,4,8,11-tetraazaundecane, aepn = N-(2-aminoethyl)-1,3-propanediamine, pmedien = N,N,N′,N″,N″-pentamethyldiethylenetriamine and DPA = di(2-pyridylmethyl)amine were synthesized and structurally characterized by X-ray crystallography. The spectral and structural characterization as well as the magnetic behaviour of these complexes is reported. In this series, structures consist of the groups as counter ions and the bridging the two M(II) centers in a μ-1,3- (1-3) and in a μ-1,2-bis(monodentate) (4) bonding fashions. The coordination geometry around the Ni(II) ions in 1 and 2 is six-coordinate with distorted octahedral environment achieved by N atoms of the amines and by one or two oxygen atoms from coordinated water molecules, respectively. In the Cu(II) complexes 3 and 4, a distorted square pyramidal geometry is achieved by the three N-atoms of the aepn or DPA and by an oxygen atom from a coordinated water molecule. The electronic spectra of the complexes in aqueous solutions are in complete agreement with the assigned X-ray geometry around the M(II) centers. The complexes show weak antiferromagnetic coupling with ∣J∣ = 1.8-4.2 cm−1 in the μ-1,3- bridged squarato compounds 1-3, and J = −16.1 cm−1 in the corresponding μ-1,2- bridged squarato complex 4. The magnetic properties are discussed in relation to the structural data.  相似文献   

12.
Some cobalt carboxylate (both mononuclear as well as binuclear) complexes have been prepared by using hindered hydrotris(3,5-diisopropyl-1-pyrazolyl)borate (TpiPr2) as supporting ligand. The reaction of [TpiPr2Co(NO3)] (2) with sodium benzoate resulted in the formation of acetonitrile coordinated complex [TpiPr2Co(OBz)(CH3CN)] (3) whereas the reaction of 2 with sodium fluorobenzoate gave coordinately unsaturated five coordinate complex of the type [TpiPr2Co(F-OBz)] (4). The oxidation of compound 4 in the presence of 3,5-diisopropylpyrazole resulted in the formation of a unique compound (5) where only one methine carbon of isopropyl group on pyrazole ring of hydrotris(3,5-diisopropyl-1-pyrazolyl)borate oxidized and coordinated with cobalt center. In compound 5, the binding behavior of fluorobenzoate also changes from bidentate to monodentate and the nonbonded oxygen atom formed intramolecular hydrogen bond with the hydrogen atom of the NH fragment of the coordinated . X-ray crystallography and IR studies confirmed the existence of hydrogen bonding in complex 5. The pyrazolato bridged binuclear cobalt(II) complex (6) was prepared by the reaction of hydrated cobalt(II) nitrate, 3,5-diisopropylpyrazole and sodium nitrobenzoate where, each cobalt is four coordinate. The X-ray structure of 6 showed that the NH fragment of terminally coordinated formed intramolecular hydrogen bonding with nonbonded oxygen atom of monodentately coordinated nitrobenzoate.  相似文献   

13.
The organometallic Lewis acid, [CpFe(CO)2]+ (Cp = η5-C5H5) reacts with excess dry diethyl ether at low temperatures to form the labile complex [CpFe(CO)2(Et2O)]+[BF4] (1) which is stable at low temperatures and has been fully characterized. Complex 1 in turn reacts with 1-aminoalkanes and α,ω-diaminoalkanes to form new complexes of the type [CpFe(CO)2NH2(CH2)nCH3]BF4 (n = 2-6) (2) and [{CpFe(CO)2}2μ-(NH2(CH2)nNH2)](BF4)2 (n = 2-4) (3), respectively. These complexes have been fully characterized and the mass spectral patterns of complexes 2 are reported. The structures of compounds 2a (n = 2) and 2b (n = 3) have been confirmed by single crystal X-ray crystallography. The single crystal X-ray diffraction data show that complex 2a, [CpFe(CO)2NH2(CH2)2CH3]BF4, crystallizes in a triclinic space group while 2b, [CpFe(CO)2NH2(CH2)3CH3]BF4, crystallizes in an orthorhombic Pca21 space group with two crystallographically independent molecular cations in the asymmetric unit. Furthermore, the reaction of 1 with 1-alkenes gives the η2-alkene complexes in high yield.  相似文献   

14.
Complexes possessing a soft donor η6-arene and hard donor acetylacetonate ligand, [(η6-p-cymene)Ru(κ2-O,O-acac-μ-CH)]2[OTf]2 (1) (OTf = trifluoromethanesulfonate; acac = acetylacetonate) and {Ar′ = 3,5-(CF3)-C6H3}, were prepared and fully characterized. The lability of the μ-CH linkage for complex 1 and the THF ligand of 2 allow access to the unsaturated cation [(η6-p-cymene)Ru(κ2-O,O-acac)]+. The reaction of with KTp {Tp = hydridotris(pyrazolyl)borate} produces . The azide complex forms upon reaction of with N3Ar (Ar = p-tolyl), and reaction of with CHCl3 at 100 °C yields the chloride-bridged binuclear complex . The details of solid-state structures of [(η6-p-cymene)Ru(κ2-O,O-acac-μ-CH)]2[OTf]2 (1), and are disclosed.  相似文献   

15.
Reaction of CuCl2 · 2H2O with the 1:1 condensate (L) of 2-(2-aminoethyl)pyridine and 1-methyl-2-imidazolecarboxaldehyde in methanol yields monomeric CuLCl2.H2O (1). Recrystallisation of 1 from aqueous methanol medium containing excess of affords the 1D coordination polymer [CuLCl]n(PF6)n (2). A chloride bridge results in the coordination polymer. A face-to-face interaction is observed between the imidazole rings in 2. The interaction influences the structure and magnetic properties of 2 markedly. The complex 2 is ferromagnetic with a J value of 1.79 ± 0.01 cm−1. The imidazole fragments in 2 are coordinated to the metal. In mononuclear (ClO4)2, where L′′ is the 1:2 condensate of ethylenediamine and 1-methyl-2-imidazolecarboxaldehyde, the imidazolyl moieties are not under the direct influence of the metal. Here the imidazole-imidazole interaction is angular and more distant.  相似文献   

16.
A facile synthetic procedure has been used to prepare one five-coordinate and four six-coordinate copper(II) complexes of 4′-chloro-2,2′:6′,2″-terpyridine (tpyCl) ligand with different counterions (, , , , and ) in high yields. They are formulated as [Cu(tpyCl-κ3N,N,N′′)(SO4-κO)(H2O-κO)] · 2H2O (1), trans-[Cu(tpyCl-κ3N,N,N″)(NO3-κO)2(H2O-κO)] (2), [Cu(tpyCl-κ3N,N,N″)2](BF4)2 (3), [Cu(tpyCl-κ3N,N,N″)2](PF6)2 (4) and [Cu(tpyCl-κ3N,N,N″)2](ClO4)2 (5) and versatile interactions in supramolecular level including coordinative bonding, O-H?O, O-H?Cl, C-H?F, and C-H?Cl hydrogen bonding, π-π stacking play essential roles in forming different frameworks of 1-5. It is concluded that the difference of coordination abilities of the counterions used and the experimental conditions codominate the resulting complexes with 1:1 or 1:2 ratio of metal and ligand.  相似文献   

17.
The synthesis of the diruthenium(II) compounds [Ru2(μ-O2CR)4(MeOH)2] [R = Me (1), Ph (2), CMePh2 (3) C6H4-p-OMe (4), C6H4-p-CMe3 (5)] by reaction of with hydroquinone, under a nitrogen atmosphere, in the presence of a base is described. This reaction constitutes an easy via to the preparation of diruthenium(II) compounds. The structure of the complexes [Ru2(μ-O2CMe)4(MeOH)2] (1) and [Ru2(μ-O2CPh)4(thf)2] (2b) is established by single crystal X-ray diffraction. These compounds show a diruthenium(II) unit bridged by four carboxylate ligands with the axial positions occupied by methanol and tetrahydrofuran molecules for 1 and 2b, respectively. Complex 1 shows, in the solid state, polymeric chains in which the molecules [Ru2(μ-O2CMe)4(MeOH)2] are linked by hydrogen bonds.  相似文献   

18.
A new family of tridentate ligands PhimpH (2-((2-phenyl-2-(pyridin-2-yl)hydazono)methyl)phenol), N-PhimpH (2-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)napthalen-1-ol), Me-PhimpH (2-(1-(2-phenyl-2-(pyridine-2-yl)hydrazono)ethyl)phenol) have been synthesized and characterized. The ligands PhimpH and N-PhimpH after deprotonation react with manganese(II) and manganese(III) starting materials affording [Mn(Phimp)2] (1), [Mn(Phimp)2](ClO4) (2), [Mn(N-Phimp)2] (3), [Mn(N-Phimp)2](ClO4) (4). Complexes [Mn(Phimp)2] (1) and [Mn(N-Phimp)2] (3) convert to [Mn(Phimp)2]+ (cation of 2) and [Mn(N-Phimp)2]+ (cation of 4) respectively upon oxidation. Ligand Me-PhimpH stabilized only manganese(III) centre resulting [Mn(Me-Phimp)2](ClO4) (5). The molecular structures of [Mn(Phimp)2], 1 and [Mn(Phimp)2](ClO4), 2 were determined by single crystal X-ray diffraction. X-ray crystal structures of 1 and 2 have revealed the presence of distorted octahedral MnN4O2 coordination sphere having meridionally spanning ligands. Electrochemical studies for the complexes showed Mn(II)/Mn(III), (E1/2 = 0.14-0.40 V) and Mn(III)/Mn(IV), (E1/2 = 0.80-1.06 V) couples vs. Ag/AgCl. The redox properties were exploited to examine superoxide dismutase (SOD) activity using Mn(II)/Mn(III) couple. The complexes 1, 2, 4 and 5 have been revealed to catalyze effectively the dismutation of superoxide () in xanthine-xanthine oxidase-nitro blue tetrazolium assay and IC50 values were found to be 0.29, 0.39, 1.12 and 0.76 μM respectively. DNA interaction studies with complex 2 showed binding of DNA in a non-intercalative pathway. Complexes 1, 2 and 4 exhibited nuclease activity in presence of H2O2 and inhibition of activity was noted in presence of KI.  相似文献   

19.
Coordination polymers Cu(l-Pro)(ClO4)(H2O)2 (1) and Cu3(Gly)4(H2O)2(NO3)2 (2) were synthesized and characterized structurally. Compound 1 possesses the structure of 1D chain, where Cu(II) ions are linked by carboxyl-group in syn-anti conformation in equatorial-equatorial mode. Compound 2 is polymeric chain, consisting from trinuclear blocks Cu3(Gly)4(H2O)22+. In each of these units Cu(II) ions are linked by carboxyl-group in the same way as in 1, while trinuclear units Cu3(Gly)4(H2O)22+ are linked by NO3 ions, acting as the bridges between Cu(II) ions of neighboring trinuclear units. Circular dichroism properties of 1 were studied in solid state and solution. Magnetic measurements revealed that there were ferromagnetic exchange interactions between Cu(II) ions in 1 (J = +1.22(1) cm-1 for Hamiltonian ) and 2 (J = +1.17(2) cm-1 for Hamiltonian ).  相似文献   

20.
The macrocycles L1-L3 having N2S2O-, N2S2-, and N2S3-donor sets, respectively, and incorporating the 1,10-phenanthroline unit interact in EtOH and MeCN solutions with CuII to give 1:1 [M(L)]2+ complex species. The compounds [Cu(L1)(ClO4)]ClO4 (1), [Cu(L2)(ClO4)]ClO4 ·  (2) and [Cu(L3)](ClO4)2 (3) were isolated at the solid state and the first two also characterised by X-ray diffraction studies. The conformation adopted by L1 and L2 in the cation complexes reveals the aliphatic portion of the rings folded over the plane containing the heteroaromatic moiety with the ligands encapsulating the metal centre within their cavity by imposing, respectively, a square-based pyramidal and a square planar geometry. In both complexes, the metal ion completes its coordination sphere by interacting with a ClO4 ligand. The compound [Cu(L3)2](PF6)2 (4) containing a 1:2 cation complex was also isolated at the solid state: EPR spectroscopy measurements suggest the presence of a CuN4 chromophore in this complex. The EPR and electronic spectral features of 1-4 have been studied and their redox properties examined in comparison with those observed for Type-1 blue copper proteins.The reactivity of L1-L3 has also been tested toward stoichiometric amounts of the CuI salt [CuCl(PPh3)3].  相似文献   

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