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1.
Reaction of [Cu2L](ClO4)4 with CH3CN in acetonitrile, and Him in DMF gave cyanide and imidazolate bridged macrocyclic dinuclear copper (II) complexes with the formula [Cu2L(CN)](ClO4)3 (1) and [Cu2L(im)](ClO4)2 · 0.7Br · 0.3Cl, (2), respectively (L = N[(CH2)2NHCH2(C6H4-p)CH2NH(CH2)2]3N). In 2, each Cu(II) atom is coordinated with four macrocyclic nitrogen atoms and one imidazolate N atom, forming a slightly distorted square pyramidal geometry. Magnetic susceptibility measurements of 1 and 2 show that the two Cu(II) atoms of the binuclear unit are antiferromagnetically coupled with g = 2.148, J = −86.09 cm−1 for 1, and g = 2.047, J = −38.20 cm−1 for 2. The correlation between the structures and the J values is discussed. 相似文献
2.
《Inorganica chimica acta》2005,358(4):1141-1150
The synthesis of new oxaaza macrocyclic ligands (2-4) derived from O1,O7-bis(2-formylphenyl)-1,4,7-trioxaheptane and functionalized tris(2-aminoethyl)amine are described. Mononuclear copper(II) complexes were isolated in the reaction of the corresponding macrocyclic ligand and copper(II) perchlorate. The structure of the [Cu(2)](ClO4)2 complex was determined by X-ray diffraction analysis. The copper(II) ion is five-coordinated by all N5 donor atoms, efficiently encapsulated by the amine terminal pendant-arm, with a trigonal-bipyramidal geometry. The complexes are further characterized by UV-Vis, IR and EPR studies. The electronic reflectance spectra evidence that the coordination geometry for the Cu(II) complexes is trigonal-bipyramidal with the ligands 1 and 2 or distorted square-pyramidal with the ligands 3 and 4. The electronic spectra in MeCN solutions are different from those in the solid state, which suggest that some structural modification may occur in solution. The EPR spectrum of powder samples of the copper complex with 2 presents axial symmetry with hyperfine split at g// with the copper nuclei (I = 3/2), which is characteristic of weakly exchange coupled extended systems. The EPR parameters (g// = 2.230, A// = 156 × 10−4 cm−1 and g⊥ = 2.085) indicate a dx2-y2 ground state. The EPR spectra of the complexes with ligands 3 and 4 show EPR spectra with a poorly resolved hyperfine structure at g//. In contrast, the complex with ligand 2 shows no hyperfine split and a line shape which was simulated assuming rhombic g-tensor (g1 = 2.030, g2 = 2.115 and g3 = 2.190). 相似文献
3.
Rui-hong Zhang 《Inorganica chimica acta》2007,360(12):3651-3657
Two oxamido-bridged trinuclear complexes of formula {[(LCu)(EtOH)]2Mn(EtOH)2}(ClO4)2 (1) and {[(LCu)(EtOH)]2Co(EtOH)2}(ClO4)2 · 2H2O (2) (H2L = 2,3-dioxo-5,6:13,14-dichlorobenzo-7,12-diphenyl-1,4,8,11-tetraazacyclo-pentadeca-7,11-diene) have been synthesized and structurally characterized. The central ions of complexes 1-2 (Mn(II), Co(II)) are all bridged by macrocyclic oxamido groups. Their magnetic properties were studied by susceptibility versus temperature measurement, the best fitting of the experimental data led to J = −16.91 cm−1 for 1 and J = −27.73 cm−1 for 2. 相似文献
4.
Christopher M. MacNeill 《Inorganica chimica acta》2011,365(1):196-203
Five new isostructural two-dimensional lanthanide-based coordination polymers with the formula Ln2(F4BDC)3(DEF)2(EtOH)2-2(DEF) (Ln = Tb, 1; Gd, 2; Eu, 3; La, 4; Nd, 5; F4BDC2− = 2,3,5,6-tetrafluoro-1,4-benzenedicarboxylate ligands; DEF = N,N′-diethylformamide), have been synthesized by reaction of Ln(NO3)3 and F4BDC in a DEF/EtOH solvent mixture. The compounds were characterized by single-crystal and powder X-ray diffraction. In all cases, the metal ion is coordinated by nine oxygen atoms from two bidentate μ2-F4BDC2− ligands, two bridging μ2-F4BDC2− ligands, one μ3-F4BDC2− ligand, one DEF molecule and one EtOH molecule forming a tri-capped trigonal prism. The Ln(1) metal ion is linked to an adjacent Ln(1) metal ion through the oxygen atoms of two bridging μ2-F4BDC2− ligands and two μ3-F4BDC2− bridging ligands to form a Ln2O18 dimer. The Ln2O18 polyhedra building units are linked to each other through four F4BDC2− ligands to form 2D sheets that are held together by hydrogen bonding to form a 3D framework. Compounds 1-5 were further characterized using thermogravimetric analysis and infrared spectroscopy. Studies of the photoluminescence properties of compounds 1 and 3, as well as the catalytic activity of compounds 3-5 in the Biginelli reaction, are presented. 相似文献
5.
1,10-Phenanthroline hydrogen phthalato manganese(II) dimer [Mn2(Hphth)2(phen)4] · 2Hphth · 6H2O (1), monomeric phenanthroline phthalato manganese(II) monomer [Mn(phth)(phen)2(H2O)] · 2.5H2O (2), 2,2′-bipyridine phthalato manganese(II) polymer [Mn(phth)(bpy)(H2O)2]n (3) and 1,10-phenanthroline maleato polymer [Mn(male)(phen)(H2O)2]n · 2nH2O (4) (H2phth = o-phthalic acid, male = maleic acid, phen = 1,10-phenanthroline and bpy = 2,2′-bipyridine) have been synthesized and characterized spectroscopically and structurally. Each Mn(II) atom in dimeric 1 is octahedrally coordinated by two oxygen atoms of phthalate anions and by two cis-phenanthroline ligands. The hydrogen phthalato anion bridges the Mn(II) ions through the deprotonated carboxyl groups, while the carboxylic acid group remains free. In the monomeric 2, the Mn(II) ion is octahedrally surrounded by four nitrogen atoms from two cis-phen ligands, one carboxyl oxygen from a monodentate phth ion, and one coordinated water molecule. The dimeric phthalato complex 1 can be cleaved into monomer 2 under heating with deprotonation, and the course of the reaction can be qualitatively traced by IR spectra. The phthalate group in the complex 3 binds to two manganese atoms through the vicinal carboxyl-oxygen atoms in syn-syn bridging mode. The Mn(II) atoms are linked by the phthalate group to yield a one-dimensional chain running along the a-axis. The coordination polymer 3 can be obtained from the reaction of dichloro dibipyridine manganese with phthalate under heating. In polymer 4, the manganese atom is six-coordinated by two nitrogen atoms from phen, two oxygen atoms from the coordinated water molecules and two oxygen atoms from two different maleate dianions. Each maleato unit links two neighboring manganese atoms to yield one-dimensional chain along b-axis in bis-monodentate mode. The single-chain polymer 4 prepared at low temperature can be converted to double-chain coordination polymer [Mn(male)(phen)]n · nH2O (5) with dehydration in warm solution. 相似文献
6.
The self-assembled reaction of 2-hydroxynicotinic acid, KOH and tri-n-butyltin chloride in CH3OH and H2O (V/V = 5:1) under solvothermal condition (150 °C) affords a novel mixed tri- and dibutyltin macrocyclic complex 1. Characterization of the complex 1 was achieved using elemental analysis, IR, NMR (1H, 13C and 119Sn) spectroscopy, TGA and X-ray crystallography diffraction analysis. X-ray data revealed that it is an unusual 16-membered macrocycle containing eight tin atoms, and they can be divided into four sorts by the distinct environments, the endocyclic tin atoms are best described as five- and six-coordinate and the exocyclic tin atoms as five-coordinate. Furthermore, a 2D corrugated sheet is formed by intermolecular C-H?Cl, O-H?N and O-H?O weak interactions. 相似文献
7.
Two novel bolaamphiphile based dicarboxylic ligands L1H2 and L2H2 are synthesized by desymmetrizing aromatic anhydrides. The corresponding Cu(II) complexes [Cu(L1) · EtOH]2 (1), [Cu(L2) · (CH3CN)]2 (2) are synthesized and characterized. The crystal structure obtained for (1) and (2) indicates that they are new class of tetralactone type macrocyclic Cu(II) chelate complexes with paddle wheel Cu2-acetate cage structure. The 1:1, Cu(II) and ligand ratio leads into formation of a novel binuclear Cu(II) tetracarboxylate complexes. The macrocyclic chelate ring size in compounds 1 and 2 was altered from [15] membered to [19] membered by introducing phthalyl and diphenyl head groups as discussed in detail. The single crystal X-ray structure shows the Cu(II)?Cu(II) distance 2.613(13) Å for 1 and 2.626(13) Å for 2, the corresponding room temperature EPR spectra recorded for powdered polycrystalline samples indicate the existence of Cu(II)?Cu(II) dimeric system. 相似文献
8.
Zhong-Qiang Zhang Ru-Dan Huang Yan-Qing Xu Zhi-Wei Jiao Chang-Wen Hu 《Inorganica chimica acta》2009,362(15):5183-1524
Three new complexes, [Mn(OBt)2(H2O)4]·3H2O (1) (OBt = 1-hydroxybenzotriazole ion), [Zn2(OBt)2(BDC)(H2O)·H2O]n (2) (H2BDC = 1,4-benzenedicarboxylic acid), and [Cu3(OBt)2(BDC)(μ3-OH)2(H2O)2·2H2O]n (3) were synthesized by hydrothermal method and were characterized by elemental analysis, IR spectroscopy, TGA, XRPD, and single-crystal X-ray diffraction. The results from single-crystal X-ray diffraction indicate that 1, 2 and 3 are zero-dimensional (0D), two-dimensional (2D) and two-dimensional (2D) frameworks, respectively. In particular, there are all two crystallographically unique metal ions in the structures of complexes 2 and 3. Complex 2 possesses two helical chains in its structure. In the structure of 3, the chains that are built from tri-copper clusters and μ3-O atoms are connected with BDC2− to construct 2D grid structure. The luminescence properties of the three complexes were investigated. 相似文献
9.
Vasile Lozan 《Inorganica chimica acta》2009,362(3):793-11029
The dinuclear nickel(II) complex [Ni2L(Cl)]+ (1), where (L)2− represents a 24-membered binucleating hexamine-dithiophenolate ligand, reacts readily with primary and secondary amines RR′NH in the presence of CO2 (1 bar) to give dinuclear monoalkyl- and dialkylcarbamate complexes [Ni2L(O2CNRR′)]+ (R = H, R′ = CH2Ph (2), R = H, R′ = n-Bu (3), R = H, R′ = n-Oct (4), R = H, R′ = CH2CH2OH (5), R = R′ = Et (6), and R = R′ = CH2CH2OH (7)). Complexes 2-7 can also be prepared by the reaction of 1 with CO2(air)/amine. The carbamate complexes are hydrolyzed in methanolic solution to give the known alkylcarbonate complex [Ni2L(O2COMe)]+ (8). These conversions are less rapid than the transesterification reactions of 8, due to a less electron-demanding carboxyl C(carbamate) atom. All new complexes were either isolated as perchlorate or tetraphenylborate salts and fully characterized by elemental analysis, UV/Vis, and IR spectroscopy. The structures of 2[BPh4] and 7[BPh4] have also been determined by X-ray crystallography. They confirm the presence of μ1,3-bridging alkylcarbamate units in the products. 相似文献
10.
Four new zinc(II) cyclams of the composition {Zn(L)(tp2−) · H2O}n (1), {Zn(L)(H2bta2−) · 2H2O}n (2), [Zn2(L)2(ox2−)] 2ClO4 · 2DMF (3), and Zn(L)(H2btc−)2 · 2DMF (4), where L = cyclam, tp2− = 1,4-benzenedicarboxylate ion, H2bta2− = 1,2,4,5-benzenetetracarboxylate ion, ox2− = oxalate ion, DMF = N,N-dimethylformamide, and H2btc− = 1,3,5-benzenetricarboxylate ion, have been synthesized and structurally characterized by a combination of analytical, spectroscopic and crystallographic methods. The carboxylato ligands in the complexes 1-4 show strong coordination tendencies toward zinc(II) cyclams with hydrogen bonding interactions between the pre-organized N-H groups of the macrocycle and oxygen atoms of the carboxylato ligands. The macrocycles in 1, 2, and 4 adopt trans-III configurations with the appropriate R,R,S,S arrangement of the four chiral nitrogen centers, respectively. However, the complex 3 shows an unusual cis V conformation with the R,R,R,R nitrogen configuration. The finding of strong interactions between the carboxylato ligands and the zinc(II) ions may provide additional knowledge for the improved design of receptor-targeted zinc(II) cyclams in anti-HIV agents. 相似文献
11.
A series of pyrazole-bridged heterometallic 3d-4f complexes, [CuDy(ipdc)2(H2O)4] · (2H2O)(H3O+) (1) and [CuLn(pdc)(ipdc)(H2O)4] · H3O+ (Ln = Ho (2), Er (3), Yb (4); H3ipdc = 4-iodo-3,5-pyrazoledicarboxylic acid; H3pdc = 3,5-pyrazoledicarboxylic acid), {[Cu3Ln4(ipdc)6(H2O)16] · xH2O}n (Ln = Sm (5), x = 8.5; Ln = Eu (6), x = 7; Ln = Gd (7), Tb (8), x = 9), have been synthesized and structurally characterized. Ligand H3ipdc was in situ obtained by iodination of ligand H3pdc. Complexes 1-4 are pyrazole-bridged heterometallic dinuclear complexes, and 2-4 are isostructural. Complexes 5-8 are isostructural and comprised of an unusual infinite one-dimensional tape-like chain based on pyrazole-bridged heterometallic dinuclear units. The magnetic properties of compounds 1-4, 7 and 8 have been investigated through the magnetic measurement over the temperature range of 1.8-300 K. 相似文献
12.
Shi-bin Wang Dai-zheng Liao Zong-hui Jiang Shi-ping Yan 《Inorganica chimica acta》2005,358(9):2595-2601
Based on the complex ligand (CuL H2L = 2,3-dioxo-5,6:15,16-dibenzo-1,4,8,13-tetraazacyclotetradeca-7,13-diene), which includes macrocyclic oxamido bridge, three trinuclear complexes were prepared. They are of the formula [(CuL)2M(ClO4)2] (M = Co(1), Ni(2)) and [(CuL)2Zn(CH3OH)2] · (ClO4)2 (3). The crystal structures of the three complexes have been determined and the M(II) of the three complexes all exist on the mirror plane. Complex 1 is the first Cu-Co complex bridged by oxamido. Their magnetic properties were studied by susceptibility versus temperature measurement, the best fitting of the experimental data led to J = −28.12 cm−1 for 1, J = −42.88 cm−1 for 2, and J = −2.13 cm−1 for 3. 相似文献
13.
Six lanthanide two-dimensional network coordination polymers with the general formula of [Ln(pmida)(NO3)(H2O)]n, where Ln = La (1), Nd (2), Sm (3), Gd (4), Dy (5), Er (6) and pmida2− = N-(2-pyridylmethyl)iminodiacetate, have been synthesized by hydrothermal process and characterized by elemental analysis, Infrared spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. All crystals are isostructural and crystallize in the monoclinic space group P21/a. The lanthanide(III) ion is nine-coordinated in a geometry of distorted tricapped trigonal prism by two N atoms and two O atoms from one pmida2− ligand, two bridging carboxylate O atoms from other two pmida2− ligands, two O atoms of a bidentate chelating nitrate and a O atom of a coordinated water molecule. The luminescent properties of [Sm(pmida)(NO3)(H2O)]n (3) and [Dy(pmida)(NO3)(H2O)]n (5) were investigated. 相似文献
14.
Lamei Wu 《Inorganica chimica acta》2007,360(9):3069-3074
A chiral Schiff base N-(S)-2-(6-methoxylnaphthyl)-propanoyl-N′-(2-hydroxylbenzylidene)hydrazine (H2L) has been synthesized. Reaction of H2L with Cu(OAc)2 · H2O led to the formation of a metal complex {[CuL] · H2O · 2DMF}∞ (1). In complex 1, the potential dinegative tridentate L2− ligand acting as tetradentate bridging ligand coordinate to two metal ions so as to form a novel infinite metal-organic coordination chain structure. The enantiomerically pure ligand H2L presents two different sets of signals in the 1H NMR spectrum either in chloroform solution or in dimethylsulfoxide solution, showing the presence of both (E) and (Z) isomers. The X-ray structural investigations of H2L revealed that it is the fully extended E-configuration in the solid state. 相似文献
15.
Sund C Belda O Wiktelius D Sahlberg C Vrang L Sedig S Hamelink E Henderson I Agback T Jansson K Borkakoti N Derbyshire D Eneroth A Samuelsson B 《Bioorganic & medicinal chemistry letters》2011,21(1):358-362
Two types of P1-P3-linked macrocyclic renin inhibitors containing the hydroxyethylene isostere (HE) scaffold just outside the macrocyclic ring have been synthesized. An aromatic or aliphatic substituent (P3sp) was introduced in the macrocyclic ring aiming at the S3 subpocket (S3sp) in order to optimize the potency. A 5-6-fold improvement in both the Ki and the human plasma renin activity (HPRA)IC50 was observed when moving from the starting linear peptidomimetic compound 1 to the most potent macrocycle 42 (Ki = 3.3 nM and HPRA IC50 = 7 nM). Truncation of the prime side of 42 led to 8-10-fold loss of inhibitory activity in macrocycle 43 (Ki = 34 nM and HPRA IC50 = 56 nM). All macrocycles were epimeric mixtures in regard to the P3sp substituent and X-ray crystallographic data of the representative renin macrocycle 43 complex showed that only the S-isomer buried the substituent into the S3sp. Inhibitory selectivity over cathepsin D (Cat-D) and BACE-1 was also investigated for all the macrocycles and showed that truncation of the prime side increased selectivity of inhibition in favor of renin. 相似文献
16.
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
17.
Complexes of the type (η4-BuC5H5)Fe(CO)2(P) (P = PPh2Py 3, PPhPy24, PPy35; Py = 2-pyridyl) were satisfactorily prepared. Upon treatment of 3 with M(CO)3(EtCN)3 (M = Mo, 6a; W, 6b), the pyridyl N-atom could be coordinated to the metal M, which then eliminates a CO ligand from the Fe-centre and induced an oxidative addition of the endo-C-H of (η4-BuC5H5). This results in a bridged hydrido heterodimetallic complex [(η5-BuC5H4)Fe(CO)(μ-P,N-PPh2Py)(μ-H)M(CO)4] (M = Mo, 7a, 81%; W, 7b, 76%). The reaction of 4 or 5 with 6a,b did not give the induced oxidative addition, although these complexes contain more than one pyridyl N-atom. The reaction of 4 with M(CO)4(EtCN)2 (M = Mo, 9a; W, 9b) produced heterodimetallic complexes [(η4-BuC5H5)Fe(CO)2(μ-P:N,N′-PPhPy2)M(CO)4] (M = Mo, 10a, 81%; W, 10b, 83%). Treatment of 5 with 6a,b gave [(η4-BuC5H5)Fe(CO)2(μ-P:N,N′,N″-PPy3)M(CO)3] (M = Mo, 12a, 96%; W, 12b, 78%). 相似文献
18.
A series of organotin(IV) complexes with Schiff base ligand pyruvic acid 3-hydroxy-2-naphthoyl hydrazone [R2SnLY]2, L = 3-HO-C10H6-2-CONHNC(CH3)COOH, R = n-C4H9, Y = CH3OH (1), R = n-C4H9, Y = N (2), R = PhCH2 (3), R = Ph, Y = CH3OH (4), R = Me, (5) and [R3SnLY], L = 3-HO-C10H6-2-CONHNC(CH3)COOH, R = n-C4H9, Y = H2O, (6), R = Ph (7), R = Me (8) have been synthesized. These complexes have been characterized by elemental analysis, IR, 1H and 119Sn NMR spectra. The crystal and molecular structure of complexes 1, 2 and 6 have been determined by X-ray single crystal diffraction. Results showed that complex 1 has a dimeric structure and the central tin atom is rendered seven-coordinate in a distorted pentagonal-bipyramid configuration. The complex 2 has a monoclinic structure and the central tin atom is rendered six-coordinate in octahedrally configuration with a planar of SnO3N unit and two apical aryl C atoms. And the whole structure consists of molecular units connected by weak intermolecular Sn?N and O-H?N interactions. In the complex 6, the central tin atom is five-coordinate in distorted trigonal-bipyramidal geometry. 相似文献
19.
M. Cristina Cassani 《Inorganica chimica acta》2005,358(5):1595-1604
The preparation of a series of 1,2-phenylenedioxoborylcyclopentadienyl-metal complexes is described. These are of formula [M{η5-C5H4(BX)}Cl3] [M = Ti and X = CAT (2a), CATt (2b) or CATtt (2c); X = CATtt and M = Zr (4a) or Hf (4b)], [M{η5-C5H4(BX)}2Cl2] [M = Zr, X = CAT (3a) or CATt (3c); or M = Hf, X = CAT (3b) or CATt (3d)], [M{(μ-η5-C5H3BCAT)2 SiMe2}Cl2] [M = Zr (5a) or Hf (5b)], [M{η5-C5H3(BCAT)2}Cl3] [M = Zr (6a) or Hf (6b)], [M{η5-C5H4BCAT}3(THF)] [M = La (7a), Ce (7b) or Yb (7c)], [Sn{η5-C5 H4(BCATt)}Cl](8) and [Fe{η5-C5H4(BCATt)}2] (9). The abbreviations refer to BO2C6H4-1,2 (BCAT) and the 4-But (BCATt) and the (BCATtt) analogues. The compounds 2a-9 have been characterised by microanalysis, multinuclear NMR and mass spectra. The single crystal X-ray structure of the lanthanum compound 7a is presented. 相似文献
20.
The preparation, crystal structures, and magnetic properties of two rhenium(IV) mononuclear compounds of formula NBu4[ReX5(DMF)] with X = Cl (1) and Br (2) are reported. 1 and 2 are isostructural complexes which crystallize in the monoclinic system with the space group P21/n. The rhenium atom is six-coordinated with five X atoms and a DMF molecule forming a somewhat distorted octahedral surrounding [values of Re-X varying in the ranges 2.317(1)-2.358(1) (1) and 2.495(1)-2.518(1) Å (2)]. Magnetic susceptibility measurements on 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. 20.2 and 39.2 cm−1 for 1 and 2, respectively). 相似文献