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1.
The X-ray structure is reported for the complex Cu2(medpco-2H)Cl2, (medpco = N,N′-bis-N,N-dimethylaminoethyl)pyridine-2,6-dicarboxamide 1-oxide. The complex is triclinic,
, a=8.313(4), B=11.403(5), C=11.611(3) Å, =91.66(3), β=108.99(4), γ=109.60(3)° and Z=2. The deprotonated ligand (medpco-2H)2− acts as a binulceating ligand, producing an N-oxide-bridged complex. Each copper in Cu2(medpco-2H)Cl2 is five-coordinate, being coordinated by a bridging N-oxide oxygen, a deprotonated amide nitrogen, a tertiary amine nitrogen and two bridging chlorides. The complex does not exhibit significant magnetic interaction, and this may be the result of distortion of the bridging geometry from planarity. A range of other, apparently N-oxide-bridged, complexes of the type Cu2(medpco-2H)X2 is reported. The complex Cu2(medpco-2H)Br2·H2O is strongly antiferromagnetic, with magnetic data closely fitting the expected binuclear structure. 相似文献
2.
Anthony T. Baker Jeffrey K. Crass Mina Maniska Donald C. Craig 《Inorganica chimica acta》1995,230(1-2):225-229
The ligand 1,2-bis(3,5-dimethylpyrazol-1-yl)ethane has been synthesized by the direct reaction of 1,2-dibromoethane and 3,5-dimethylpyrazole. The complex of this ligand with palladium(II) chloride has been prepared and the structure of its toluene solvate has been determined by X-ray crystallography. The compound crystallises in the triclinic space group
, a = 11.088(5), B = 13.786(5), C = 21.169(9) Å, = 86.96(3), β = 81.02(3), γ = 73.32(3)° with Z = 2. Final residuals after least-squares refinement: R = 0.030, Rw = 0.039. The compound has a trimeric structure which may be described as a ‘molecular tricorn’: the ligand bridges adjacent palladium centres, giving rise to a 21-membered trimetallic macrocycle. The overall structure closely approximates D3 symmetry with approximate two-fold axes passing through each palladium atom and the centre of the 1,2-ethanediyl moiety opposite. An interesting feature of the structure is the close approach of several hydrogen atoms from the 1,2-ethanediyl groups to each palladium centre; these interactions are thought to be close-packing rather than agostic bonds. 相似文献
3.
The preparation, crystal structures and magnetic properties of three copper(II) compounds of formulae [Cu2(dmphen)2(dca)4] (1), [Cu(dmphen)(dca)(NO3)]n (2) and [Cu(4,4′-dmbpy)(H2O)(dca)2] (3) (dmphen=2,9-dimethyl-1,10-phenanthroline, dca=dicyanamide and 4,4′-dmbpy=4,4′-dimethyl-2,2′-bipyridine) are reported. The structure of 1 consists of discrete copper(II) dinuclear units with double end-to-end dca bridges whereas that of 2 is made up of neutral uniform copper(II) chains with a single symmetrical end-to-end dca bridge. Each copper atom in 1 and 2 is in a distorted square pyramidal environment: two (1) or one (2) nitrile-nitrogen atoms from bridging dca groups, one of the nitrogen atoms of the dmphen molecule (1 and 2) and either one nitrile-nitrogen from a terminal dca ligand (1) or a nitrate-oxygen atom (2) build the equatorial plane whereas the second nitrogen atom of the heterocyclic dmphen fills the axial position (1 and 2). The copper-copper separations through double (1) and single (2) end-to-end dca bridges are 7.1337(7) (1) and 7.6617(7) (2). Compound 3 is a mononuclear copper(II) complex whose structure contains two neutral and crystallographically independent [Cu(4,4′-dmbpy)(H2O)(dca)2] molecules which are packed in two different layer arrangements running parallel to the bc-plane and alternating along the a-axis. The copper atoms in both molecules have slightly distorted square pyramidal surroundings with the two nitrogen atoms of the 4,4′-dmbpy ligand and two dca nitrile-nitrogen atoms in the basal plane and a water oxygen in the apical position. A semi co-ordinated dca nitrile-nitrogen from a neighbour unit [2.952(6) Å for Cu(2)-N] is in trans position to the apical water molecule in one of the two molecules, this feature representing part of the difference in supramolecular connections in the alternating layers referred to above. Magnetic susceptibility measurements for 1-3 in the temperature range 1.9-290 K reveal the occurrence of weak antiferromagnetic interactions through double [J=−3.3 cm−1 (1), ] and single [J=−0.57 cm−1 (2), ] dca bridges and across intermolecular contacts [θ=−0.07 K (3)]. 相似文献
4.
Sukanta Mandal 《Inorganica chimica acta》2006,359(12):4019-4026
The ligand 1,3-bis[(2-dimethylaminoethyl)iminomethyl]benzene (baib) reacts with [Cu(MeCN)4][ClO4] to form a binuclear copper(I) complex . Crystal structure analysis reveals that the distorted tetrahedral coordination of each copper(I) center is satisfied by one bidentate arm of each ligand. The complex undergoes ready aromatic ring hydroxylation at position 2 of the phenyl ring when reacted with molecular oxygen in MeCN/MeOH/CH2Cl2, producing a four-coordinate μ-phenoxo- and μ-hydroxo-bridged dicopper(II) complex, [Cu2(baib-O)(OH)(OClO3)2] · 1.5H2O (2) (baib-OH: 1,3-bis[(2-dimethylaminoethyl)iminomethyl]phenol). This reaction mimics the reactivity of the copper monooxygenase tyrosinase. A trend is observed for the extent of aromatic ring hydroxylation (25 °C): MeCN > MeOH > CH2Cl2. Cyclic voltammetric experiment of 1 in MeCN reveals an appreciably high redox potential (anodic peak potential, Epa = 0.69 V versus SCE) for the redox process. Complex 2 has been characterized by single-crystal X-ray crystallography. Variable temperature (60-300 K) magnetic susceptibility measurements on 2 establish that the copper(II) centers in 2 are antiferromagnetically coupled (2J = −280 cm−1). 相似文献
5.
Achilleas Garoufis Spyros P. Perlepes Andrew Vreugdenhil Ian S. Butler Nick Hadjiliadis 《Inorganica chimica acta》1995,240(1-2):673-677
The first 1:2 metal complexes of 2-(2′-pyridyl)quinoxaline (L) have been isolated. The physical and spectroscopic characteristics of the compounds [MCl2L2] (M = Ni, Cu, Cd) and [CuIL2](PF6) are described. The structure of the copper(I) complex has been determined by X-ray diffraction methods. Crystals are orthorhombic, space group Pcnb with A = 11.014(2), B = 12.886(2), C = 17.806(4) Å, V = 2527.1(9) Å3 and Z = 4. Refinement of the structure gave a final R factor of 0.046 (Rw = 0.041) for 814 unique reflections having I > 2.0σ(I). The ligand L acts as a bidentate chelate, the ligated atoms being the pyridine nitrogen and the nearest quinoxaline nitrogen. The structure of [CuL2]+ consists of a distorted tetrahedral arrangement around the copper(I) atom with Cu---N bond lengths of 2.023(6) and 2.059(5) Å and the N---Cu---N angle of the chelating ligand equal to 80.6(2)°. A monomeric trans pseudo-octahedral stereochemistry is assigned for the [MCl2L2] complexes. 相似文献
6.
The compound 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra-(2-bromoethoxy)calix[4]arene has been prepared by first converting 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra-(2-hydroxyethoxy)calix[4]arene into the tosylate, and then to the product by reaction with LiBr. The compound crystallizes in the trigonal space group P3221 with A = 13.160(2), C = 25.595(6) Å, A = 90.00(2), β = 90.00(1), γ = 120.000(9)0, Z = 3, calc = 1.40 g cm−3. The final R value for 2391 unique reflections was 0.061. The compound reacts with excess sodium N,N-dimethyldithiocarbamate to give 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra-(2-N,N-dimethyldithiocarbamoylethoxy)calix[4]arene. This compound is an effective extractant for transferring palladium(II) from an aqueous to a chloroform phase. No extraction of PtCl42− is observed under thermal conditions. Under photochemical conditions using a mixture of PtCl42− and PtCl62−, extraction of platinum into the chloroform layer is observed. An explanation for this observation is given. 相似文献
7.
J.A. García-Vázquez J. Romero R. Castro A. Sousa D.J. Rose J. Zubieta 《Inorganica chimica acta》1997,260(2):2900-223
(3-Trimethylsilyl-pyridine-2-thiolato-S,N)copper(I), [Cu(3-Me3Sipyt)], was obtained by electrochemical oxidation of copper metal in an acetonitrile solution of the neutral ligand. The compound is tetrameric and the four copper atoms are arranged with distorted tetrahedral geometry, each copper atom being trigonally coordinated to one nitrogen and two sulfur atoms of three different ligands. Crystal data: 141/a, a=14.608(2), C=19.366(4) Å, V=4133(2), Å, Z=4, Dcalc=1.581 g cm−3, R=0.0397 for 848 reflections. 相似文献
8.
Kaspar Hegetschweiler Michael Wrle Marc D. Meienberger Reinhard Nesper Helmut W. Schmalle Robert D. Hancock 《Inorganica chimica acta》1996,250(1-2):35-47
The interaction of 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and its N-methylated derivative 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci) with the incomplete [Mo3S4]4+ cube and the heterometallic [Mo3S4Cu]4+ cube have been investigated by X-ray analysis. The crystal structures of [Mo3S4(taci+ rmC3H6O-H2O)3-4H]·2OH2O (1a, rhombohedral, space group R32, A = 15.964(3), C = 40.59(1) Å, Z = 6), [Mo3S4(tdci)3]Br4·9.5EtOH·5H2O (2a, triclinic, space group and [CuBrMo3S4(tdci)3]Br3·11 H2O·EtOH (3a, monoclinic, space group P2,/n, A = 14.887(3), B = 22.570(4), C = 21.974(5) Å, β = 98.54(2)°, Z = 4) revealed andN-N-O and an N-O-O coordination mode for taci and tdci, respectively. In 1a, taci is coordinated as an anion with deprotonated oxygen and nitrogen donors. In addition, the non-coordinating amino group reacted with one equivalent; of acetone, forming a Schiff base condensation product. For 2a, short Mo---O bonds and high pKa values (compared to the aqua ion [Mo3S4(H2O)9]4+) indicate the formation of a zwitterionic form of the tdci ligand with coordinated alkoxo groups and peripheral dimethylammonium groups. No significant differences were found for the structural properties of the Mo-tdci fragment in 2a and 3a. The coordination modes of taci and tdci, as observed in the solid state, are in agreement with the previously reported solution structures, established by NMR spectroscopy. They are attributed to the specific steric requirements of the two ligands and to a pronounced preference of the [Mo3(μS)3(μ3S)]4+ core to coordinate a nitrogen donor trans to μ3S. 相似文献
9.
New mixed metal complexes SrCu2(O2CR)3(bdmap)3 (R = CF3 (1a), CH3 (1b)) and a new dinuclear bismuth complex Bi2(O2CCH3)4(bdmap)2(H2O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi2O3 at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm−1. Crystal data for 1a: C27H51N6O9F9Cu2Sr/THF, monoclinic space group P21/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å3, Z = 2; for 1b: C27H60N6O9Cu2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å3, Z = 8; for 2: C22H48O11N4Bi2, monoclinic space group P21/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å3, Z = 4. 相似文献
10.
Two new rhenium(IV) mononuclear compounds of formula NBu4[ReBr4(OCN)(DMF)] (1) and (NBu4)2[ReBr(OCN)2(NCO)3] (2) (NBu4 = tetrabutylammonium cation, OCN = O-bonded cyanate anion, NCO = N-bonded cyanate anion and DMF = N,N-dimethylformamide) have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. 1 crystallizes in the monoclinic system with the space group P21/n, whereas 2 crystallizes in the triclinic one with as space group. In both complexes the rhenium atom is six-coordinated, in 1 by four Br atoms in the equatorial plane, and two trans-oxygen atoms, one of a DMF molecule and another one from a cyanato group, while in 2 by one bromide anion and five cyanate ligands, two of which are O-bonded and three N-bonded, forming a somewhat distorted octahedral surrounding. Magnetic susceptibility measurements on polycrystalline samples of 1 and 2 in the temperature range 1.9-300 K are interpreted in terms of magnetically isolated spin quartets with large values of the zero-field splitting (|2D| is ca. 41.6 and 39.2 cm−1 for 1 and 2, respectively). 相似文献
11.
The ligand 1,4,7-triazacyclononane-1,4,7-tris[2′(R)-2′-propionate](-3)((R)-tacntp3−), binds stereospecifically to transition metal ions. The structures of the complexes [Cr((R)-tacntp)]·NaBr and [Fe((R)-tacntp)]·H2O have been determined by X-ray crystallography. Both complexes have the Λ-configuration but the conformation of the chelate rings in Λ-[Cr((R)-tacntp)] is (λ,λ,λ) with a geometry close to octahedral while in Λ-[Fe((R)-tacntp)] it is (δ,δ,δ) and the geometry is closer to that of a trigonal prism. Chiral induction in the electron transfer reactions of Λ-[Co((R)-tacntp)], Λ-[Fe((R)-tacntp)] and Λ-[Mn((R)-tacntp)] with [Co((RR,SS)-chxn)3]2+ has been investigated. All three reactions are outer-sphere and four isomeric [Co((RR,SS)-chxn)3]3+ products are identified in each case. The oxidants Λ-[Fe((R)-tacntp)] and Λ-[Mn((R)-tacntp)] show very similar selectivities, quite different from those of Λ-[Co((R)-tacntp)]. Reasons for this behavior are discussed. 相似文献
12.
The crystal structure of the title compound [Fe(bpz)3](ClO4)2 · H2O (bpz=2,2′-bipyrazine) has been determined by a single crystal X-ray diffraction study at 293(2) K. The complex is monoclinic, P21/c, a=17.263(3), b=9.983(2), c=17.921(4) Å, β=107.94(3)°, V=2938.3(10) Å3, Z=4, R=0.073 and Rw=0.118. The structure is made up of tris-chelated [Fe(bpz)3]2+ cations, uncoordinated perchlorate anions and crystallization water molecules. The iron atom exhibits a FeN6 distorted octahedral geometry with average Fe-N bond length and N-Fe-N bidentate angle of 1.962(5) Å and 81.6(2)°. The value of the Fe-N bond distance and that of the room temperature magnetic moment are in agreement with a singlet 1A1 ground state. The structure of 1 is compared to those of other tris-chelated iron(II) complexes with bidentate nitrogen heterocycles. 相似文献
13.
Giovanni De Munno Miguel Julve Jos Antonio Real Francesc Lloret Rosario Scopelliti 《Inorganica chimica acta》1996,250(1-2):81-85
The iron(II) compound of formula [Fe(bpym)(NCS)2]n (bpym = 2,2′-bipyrimidine) has been synthesized and its crystal structure determined by X-ray diffraction methods. It crystallizes in the tetragonal P41 (No. 76) and P43 space groups, a = 8.849(2), C=16.486(3) Å, V=1290.9(5) Å3, Z=4, Dc=1.699 g cm−3, Mr=330.2, F(000)=664, λ(Mo K)=0.71073 Å, μ(Mo K)=14.8 cm−1 and T=295 K. A total of 2449 reflections was collected over the range 3≤2≤55°; of these, 1657 were unique and 1321 were considered as observed (13σ(I)) and used in the structural analysis. The final R and Rw residuals were 0.027 and 0.026, respectively. The structure is made up of chiral (Δ and Λ enantiomers crystallize in the same crop) chains of iron(II) atoms bridged by bis-chelating bpym, the electroneutrality being achieved by N-bonded thiocyanato groups in cis position. Each metal atom is in a distorted FeN6 octahedral environment, the Fe---N bonds ranging from 2.265(3) to 2.028(4)
. The intrachain metal-metal separation is 5.960(1) Å. Variable-temperature magnetic susceptibility data in the temperatyre range 290–4.2 K show that the iron(II) is high-spin and interacts in an antiferromagnetic fashion, the relevant parameters being . The magnitude of the exchange coupling compares well with that reported for other structurally characterized bpym-bridged iron(II) complexes. 相似文献
14.
Jorunn Sletten Miguel Julve Francesc Lloret Isabel Castro Gunther Seitz Klaus Mann 《Inorganica chimica acta》1996,250(1-2):219-225
The first crystal and molecular structure of a transition metal complex containing 1,2-dithiocroconate (1,2-dtcr, dianion of 1,2-dimercaptocylopent-1-ene-3,4,5-trione), [Cu(bpca)(H2O)]2[Cu(1,2-dtcr)2]·2H2O (where bpca is the bis(2-pyrdidylcarbonyl)amide anion), has been determined by single crystal X-ray diffraction methods. The compound crystallizesin the monoclinic syste, space group P21/c, with a = 11.661(3), b = 20.255(6), c = 8.265(3) Å, ß = 107.26(2)° and Z = 2. The structure is formally built of [Cu(1,2-dtcr)2]2− and [Cu(bpca)(H2O)]+ ions and water of hydration. The copper atom of the anion is situated at a crystallographic inversion centre, bonded to four sulfur atoms in a planar, approximately square arrangement. In the cation the copper equatorial plane is formed by the three nitrogen atoms of the bpca ligand and a water oxygen atom. In addition there is a very weak axial bond to one of the sulfur atoms of a 1,2-dtcr ligand in the anion. Through these latter weak bonds each anion is connected to, and sandwiched between, two cations, resulting in neutral, trinuclear, centrosymmetric formula units. The triple-decker molecules are arranged in stacks along the crystallographic a-axis creating close contacts between the terminal copper atoms and bpca groups of the neighbouring molecules. This intermolecular interaction is, however, too weak to define the structure as a chain compound. The distance between adjacent copper atoms within the trinuclear unit is 4.189(1) Å, while the shortest intra-stack metal-metal separation between terminal copper atoms is 5.281(1) Å. Variable-temperature magnetic susceptibility measurements in the temperature r.2–140 K reveal that a Curie law is followed; with three non-interacting copper(II) ions in the formula unit. 相似文献
15.
A series of luminescent tetranuclear cuboidal copper(I) diynyl complexes, [Cu4(PAr3)4(μ3-η1-CCCCR′)4] (Ar=Ph, R′=Ph, C6H4CH3-p, C6H4OCH3-p; Ar=C6H4CH3-p, C6H4F-p, R′=Ph) has been synthesized and characterized. The X-ray crystal structure of [Cu4(PPh3)4(μ3-η1-CCCCPh)4] has been determined. The origin of the low-energy emission in the complexes is assigned as derived from a metal-centered 3d94s1 state, mixed with LMCT [diynyl→Cu4] and IL [π-π*(diynyl)] states. 相似文献
16.
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
17.
Umberto Belluco Roberta Bertani Rino A. Michelin Mirto Mozzon Franco Benetollo Gabriella Bombieri Robert J. Angelici 《Inorganica chimica acta》1995,240(1-2):567-574
The chloro complexes trans-[Pt(Me)(Cl)(PPh3)2], after treatment with AgBF4, react with 1-alkynes HC---C---R in the presence of NEt3 to afford the corresponding acetylide derivatives trans-[Pt(Me) (C---C---R) (PPh3)2] (R = p-tolyl (1), Ph (2), C(CH3)3 (3)). These complexes, with the exception of the t-butylacetylide complex, react with the chloroalcohols HO(CH2)nCl (n = 2, 3) in the presence of 1 equiv. of HBF4 to afford the alkyl(chloroalkoxy)carbene complexes trans-[Pt(Me) {C[O(CH2)nCl](CH2R) } (PPh3)2][BF4] (R = p-tolyl, N = 2 (4), N = 3 (5); R=Ph, N = 2 (6)). A similar reaction of the bis(acetylide) complex trans-[Pt(C---C---Ph)2(PMe2Ph)2] with 2 equiv. HBF4 and 3-chloro-1-propanol affords trans-[Pt(C---CPh) {C(OCH2CH2CH2Cl)(CH2Ph) } (PMe2Ph)2][BF4] (7). T alkyl(chloroalkoxy)-carbene complex trans-[Pt(Me) {C(OCH2CH2Cl)(CH2Ph) } (PPh3)2][BF4] (8) is formed by reaction of trans-[Pt(Me)(Cl)(PPh3)2], after treatment with AgBF4 in HOCH2CH2Cl, with phenylacetylene in the presence of 1 equiv. of n-BuLi. The reaction of the dimer [Pt(Cl)(μ-Cl)(PMe2Ph)]2 with p-tolylacetylene and 3-chloro-1-propanol yields cis-[PtCl2{C(OCH2CH2CH2Cl)(CH2C6H4-p-Me}(PMe2Ph)] (9). The X-ray molecular structure of (8) has been determined. It crystallizes in the orthorhombic system, space group Pna21, with a = 11.785(2), B = 29.418(4), C = 15.409(3) Å, V = 4889(1) Å3 and Z = 4. The carbene ligand is perpendicular to the Pt(II) coordination plane; the PtC(carbene) bond distance is 2.01(1) Å and the short C(carbene)-O bond distance of 1.30(1) Å suggests extensive electronic delocalization within the Pt---C(carbene)---O moietry. 相似文献
18.
Antonio de León Jordi García-Antón Mercè Font-Bardía 《Inorganica chimica acta》2009,362(10):3801-4280
Complex [PdCl(bdtp)](BF4), in presence of AgBF4 or NaBF4, reacts with pyridine (py), triphenylphosphine (PPh3), cyanide (CN−), thiocyanate (SCN−) or azide (N3−) ligands, leading to the formation of the following complexes: [Pd(bdtp)(py)](BF4)2 [1](BF4)2, [Pd(bdtp)(PPh3)](BF4)2 [2](BF4)2, [Pd(CN)(bdtp)](BF4) [3](BF4), [Pd(SCN)(bdtp)](BF4) [4](BF4) and [Pd(N3)(bdtp)](BF4) [5](BF4). These complexes were characterised by elemental analyses, mass spectrometry, conductivity measurements, infrared and NMR spectroscopies. The crystal structure of [2](BF4)2 was determined by single-crystal X-ray diffraction methods. The metal atom is coordinated by two azine nitrogen atoms, and one sulfur atom of the thioether-pyrazole ligand and one triphenylphosphine in a distorted square-planar geometry. 相似文献
19.
The novel ferromagnetic coupling one-dimensional complex {Cu(NIT3Py)2[N(CN)2]2(H2O)2} (NIT3Py=2-(3′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group C2/c. The Cu(II) ion is in a distorted octahedral environment. The units of {Cu(NIT3Py)2[N(CN)2]2(H2O)2} were connected as one-dimensional structure by the intermolecular hydrogen bonds. Magnetic measurements show that there are intramolecular ferromagnetic interactions and intermolecular antiferromagnetic interactions within the chain. 相似文献
20.
Marcel Hoogenraad Kevita Ramkisoensing Willem L. Driessen Huub Kooijman Anthony L. Spek Elisabeth Bouwman Jaap G. Haasnoot Jan Reedijk 《Inorganica chimica acta》2001,320(1-2):117-126
New manganese(III) complexes of Hphox (2-(2′-hydroxyphenyl)-oxazoline) and HClphox (2-(5′-chloro-2′-hydroxyphenyl)-oxazoline) have been synthesised. The X-ray structures of [Mn(phox)2(MeOH)2][Mn(phox)2(ClO4)2](H2O)2 and [Mn(Clphox)2(MeOH)2](ClO4) show the manganese(III) ions to be octahedrally coordinated with methanol or perchlorate at the axial coordination sites. The cyclic voltammograms of the complexes, with the exception of [Mn(phox)2(acac)] (Hacac=2,4-pentanedione), show an irreversible reduction wave of manganese(III) to manganese(II). After addition of an excess of 1-methylimidazole (1-Meim), the reduction process shifts towards lower potentials and becomes (quasi-) reversible, indicating that the presence of 1-Meim affects the catalytic efficiency of the complexes. The complexes catalyse the epoxidation of styrene by dihydrogen peroxide. The cumulative turnover numbers towards styrene oxide obtained after 15 min. vary from 16 for [Mn(Clphox)2(MeOH)2](ClO4) to 26 for [Mn(phox)2(acac)]. Ligand degradation appears to be the limiting factor for obtaining higher turnover numbers. 相似文献