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1.
Six novel Cd(II) coordination polymers based on 4,4′-bis(1,2,4-triazol-1-ylmethyl)biphenyl (btmb), namely, [Cd(btmb)2I2]n (1), [Cd(btmb)I2]n (2), {[Cd(btmb)2(NO3)2]·H2O}n (3), {[Cd(btmb)2(SCN)2]·3H2O}n (4), {[Cd(btmb)(CH3COO)2(H2O)]·CH3CN}n (5) and [Cd(btmb)Cl2(H2O)]n (6) have been synthesized by the reactions of btmb with Cd(II) salts in the presence of different anions (I−, , NCS−, CH3COO− or Cl−) under appropriate reaction conditions. The assemblies of btmb with CdI2 afford two different structures: two-dimensional (2D) rhombohedral grid layer network structure 1 and 2D layer structure 2 involved with one-dimensional (1D) linear cadmium chains. Treatment of btmb with Cd(NO3)2·4H2O gives rise to a 2D grid network structure 3 which is similar to 1. When the I− or NO3− anions were replaced by NCS−, CH3COO− or Cl−, different 1D coordination polymers 4-6 were obtained, respectively. Polymer 4 displays a 1D double-chain structure, while both polymers 5 and 6 show 1D zigzag chain structures. In addition, the luminescence measurements reveal that polymers 1-6 exhibit different fluorescent emissions in the solid-state at room temperature, which can be attributed to the various coordination environments of Cd(II), solvent molecules and different packing interactions in these polymers. 相似文献
2.
Larysa Penkova Vadim A. Pavlenko Franc Meyer Igor O. Fritsky 《Inorganica chimica acta》2010,363(12):3036-8436
The synthesis, crystal structure and magnetic properties of manganese(III) binuclear complexes [MnIII2(L-3Н)2(CH3ОH)4]·2CH3ОH (1) and [MnIII2(L-3Н)2(Py)4]·2Py (2) (L = 3-[(1E)-N-hydroxyethanimidoyl]-4-methyl-1H-pyrazole-5-carboxylic acid) are reported. The ligand contains two distinct donor compartments formed by the pyrazolate-N and the oxime or the carboxylic groups. The complexes were characterized by X-ray single crystal diffraction, revealing that both 1 and 2 consist of dinuclear units in which the two metal ions are linked by double pyrazolate bridges with a planar {Mn2N4} core. Cryomagnetic measurements show antiferromagnetic interaction with g = 1.99, J = −3.6 cm−1, Θ = −2.02 K for 1 and g = 2.00, J = −3.7 cm−1, Θ = 1.43 K for 2. 相似文献
3.
The reaction of the racemic chiral methyl complex (η5-C5H5)Re(NO)(PPh3)(CH3) (1) with CF3SO3H and then NH2CH2C6H5 gives [(η5-C5H5)Re(NO)(PPh3)(NH2CH2C6H5)]+ ([4a-H]+; 73%), and deprotonation with t-BuOK affords the amido complex (η5-C5H5)Re(NO)(PPh3)(NHCH2C6H5) (76%). Reactions of 1 with Ph3C+ X− and then primary or secondary amines give [(η5-C5H5)Re(NO)(PPh3)(CH2NHRR′)]+ X− ([6-H]+ X−; R/R′/X = a, H/NH2CH2C6H5/BF4; a′, H/NH2CH2C6H5/PF6; b, H/NH2CH2(CH2)2CH3/PF6; c, H/(S)-NH2CH(CH3)C6H5/BF4); d, CH2CH3/CH2CH3/PF6; e, CH2(CH2)2CH3/CH2(CH2)2CH3/PF6; f, CH2C6H5/CH2C6H5/PF6; g, -CH2(CH2)2CH2-/PF6; h, -CH2(CH2)3CH2-/PF6; i, CH3/CH2CH2OH/PF6 (62-99%). Deprotonations with t-BuOK afford the amines (η5-C5H5)Re(NO)(PPh3)(CH2NRR′) (6a-i; 99-40%), which are more stable and isolated in analytically pure form when R ≠ H. Enantiopure 1 is used to prepare (RReSC)-[6c-H]+, (RReSC)-6c, (S)-[6g-H]+, and (S)-6g. The crystal structures of [4a-H]+, a previously prepared NH2CH2Si(CH3)3 analog, [6a′,d,f,h-H]+, (RReSC)-6c, and 6f are determined and analyzed in detail, particularly with respect to cation/anion hydrogen bonding and conformation. In contrast to analogous rhenium containing phosphines, 6a-i show poor activities in reactions that are catalyzed by organic amines. 相似文献
4.
Using a phosphorus based Mannich condensation reaction the new pyridylphosphines {5-Ph2PCH2N(H)}C5H3(2-Cl)N (1-Cl) and {2-Ph2PCH2N(H)}C5H3(5-Br)N (1-Br) have been synthesised in good yields (60% and 88%, respectively) from Ph2PCH2OH and the appropriate aminopyridine. The ligands 1-Cl and 1-Br display variable coordination modes depending on the choice of late transition-metal complex used. Hence P-monodentate coordination has been observed for the mononuclear complexes AuCl(1-Cl) (2), AuCl(1-Br) (3), RuCl2(p-cymene)(1-Cl) (4), RuCl2(p-cymene)(1-Br) (5), RhCl2(Cp∗)(1-Cl) (6), RhCl2(Cp∗)(1-Br) (7), IrCl2(Cp∗)(1-Cl) (8), IrCl2(Cp∗)(1′-Cl) (8′), IrCl2(Cp∗)(1-Br) (9), cis-/trans-PdCl2(1-Cl)2 (10), cis-/trans-PdCl2(1-Br)2 (11), cis-PtCl2(1-Cl)2 (12) and cis-PtCl2(1-Br)2 (13). Reaction of Pd(Me)Cl(cod) (cod = cycloocta-1,5-diene) with either 1 equiv. of 1-Br or the known pyridylphosphines 1′-Cl, 1-OH or 1-H gave the P/N-chelate complexes Pd(Me)Cl(1-Br-1-H) (14)-(17). All new compounds have been fully characterised by spectroscopic and analytical methods. Furthermore the structures of 4, 5, 10 and 16 · (CH3)2SO have been elucidated by single crystal X-ray crystallography. A crystal structure of the dinuclear metallocycle trans,trans-[PdCl2{μ-P/N-{Ph2PCH2N(H)}C5H4N}]2 · CHCl3, 18 · CHCl3, has also been determined. Here 1-H bridges, using both P and pyridyl N donors, two dichloropalladium centres affording a 12-membered ring with the PdCl2 units adopting a head-to-tail arrangement. 相似文献
5.
Rui-hong Zhang 《Inorganica chimica acta》2007,360(8):2835-2841
Based on self-assembly of the dissymmetrical mononuclear entity CuL(CH3OH) [H2L = (E)-N1-(2-((2-aminocyclohexydiimino)(phenyl)methyl)-4-chlorophenyl)-N2-(2-benzyl-4-chlorophenyl)oxalamide] with Mn(II), two trinuclear complexes were prepared. They are of the formula [(LCuN3)2Mn(CH3OH)2] · 2CH3OH · 2H2O (1) and [(LCuSCN)2Mn(H2O)2] · 4CH3OH (2). Their magnetic properties were studied by susceptibility versus temperature measurement, the best fitting of the experimental data led to J = −14.40 cm−1 for 1 and J = −15.48 cm−1 for 2. Hydrogen bonds help complex 1 to produce a novel S type one-dimensional chain-like supramolecular structure. In complex 2, Cl?Cl interaction also results in the formation of a one-dimensional structure. 相似文献
6.
Rodolphe F.R. Jazzar Andrew D. Burrows Stuart A. Macgregor Mary F. Mahon 《Inorganica chimica acta》2006,359(3):815-820
Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh3)2(CO)(NC4H3C(O)CH3)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (ΔH‡ = 195 ± 41 kJ mol−1; ΔS‡ = 232 ± 62 J mol−1 K−1); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2′-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions. 相似文献
7.
Daniela M. Tomazela Gunter Ebeling Marcos N. Eberlin Jairton Dupont 《Inorganica chimica acta》2004,357(8):2349-2357
Electrospray (ESI) mass spectra analysis of acetonitrile solutions of a series of neutral chloro dimers, pincer type, and monomeric palladacycles has enabled the detection of several of their derived ionic species. The monometallic cationic complexes Pd[κ1-C,κ1-N,κ1-S-C(CH3S-2-C6H4)C(Cl)CH2N(CH3)2]+ (1a) and [Pd[κ1-C,κ1-N,κ1-S-C(CH3S-2-C6H4)C(Cl)CH2N(CH3)2](CH3CN)]+ (1b) and the bimetallic cationic complex [κ1-C,κ1-N,κ1-S-C(CH3S-2-C6H4)C(Cl)CH2N(CH3)2]Pd-Cl-Pd[κ1-C,κ1-N,κ1-S-C(CH3S-2-C6H4)C(Cl)CH2N(CH3)2]+ (1c) were detected from an acetonitrile solution of the pincer palladacycles Pd[κ1-C,κ1-N,κ1-S-C(CH3S-2-C6H4)C(Cl)CH2N(CH3)2](Cl) 1. For the dimeric compounds {Pd[κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2](μ-Cl)}2 (2, Y=H and 3, CF3), highly electronically unsaturated palladacycles [Pd[κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2]+ (2d, 3d) and their mono and di-acetonitrile adducts, namely, [Pd[κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2](CH3CN)]+ (2e, 3e) and [Pd[κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2](CH3CN)2]+ (2f and 3f) were detected together with the bimetallic complex [Pd[κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2]-Cl-Pd[κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N](CH3)2]+ (2a, 3a) and its acetonitrile adducts [κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2](CH3CN)Pd-Cl-Pd[ κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2]+ (2b, 3b) and [κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2](CH3CN)Pd-Cl-Pd[κ1-C, κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2(CH3CN)]+ (2c, 3c). The dimeric palladacycle {Pd[κ1-C,κ1-N-C(CH3O-2-C6H4)C(Cl)CH2N(CH3)2](μ-Cl)}2 (4) is unique as it behaves as a pincer type compound with the OCH3 substituent acting as an intramolecular coordinating group which prevents acetonitrile full coordination, thus forming the cationic complexes [(C6H4(o-CH3O)CC(Cl)CH2N(CH3)2-κO,κC,κN)Pd]+ (4b), [(C6H4(o-CH3O)CC(Cl)CH2N(CH3)2- κO,κC,κN)Pd(CH3CN)]+ (4c) and [(C6H4 (o-MeO)CC(Cl)CH2N(CH3)2-κO, κC,κN)Pd-Cl-Pd(C6H4(o-CH3O)CC(Cl)CH2N(CH3)2-κO,κC,κN)]+ (4a). ESI-MS spectra analysis of acetonitrile solutions of the monomeric palladacycles Pd[κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2](Cl)(Py) (5, Y=H and 6, Y=CF3) allows the detection of some of the same species observed in the spectra of the dimeric palladacycles, i.e., monometallic cationic 2d-3d, 2e-3e and {Pd[κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2](Py)}+ (5a, 6a) and {Pd[κ1-C,κ1-N-C(Y-2-C6H4)C(Cl)CH2N(CH3)2](CH3CN)(Py)}+ (5b, 6b) and the bimetallic 2a, 3a, 2b, 3b, 2c and 3c. In all cationic complexes detected by ESI-MS, the cyclometallated moiety was intact indicating the high stability of the four or six electron anionic chelate ligands. The anionic (chloride) or neutral (pyridine) ligands are, however, easily replaced by the acetonitrile solvent. 相似文献
8.
Martin A. Bennett Matthew J. Byrnes Guandolina Chung Alison J. Edwards Anthony C. Willis 《Inorganica chimica acta》2005,358(5):1692-1708
Reaction of cis-[Ru(acac)2(η2-C8H14)2] (1) (acac = acetylacetonato) with two equivalents of PiPr3 in THF at −25 °C gives trans-[Ru(acac)2(PiPr3)2], trans-3, which rapidly isomerizes to cis-3 at room temperature. The poorly soluble complex [Ru(acac)2(PCy3)2] (4), which is isolated similarly from cis-[Ru(acac)2(η2-C2H4)2] (2) and PCy3, appears to exist in the cis-configuration in solution according to NMR data, although an X-ray diffraction study of a single crystal shows the presence of trans-4. In benzene or toluene 2 reacts with PiPr3 or PCy3 to give exclusively cis-[Ru(acac)2(η2-C2H4)(L)] [L = PiPr3 (5), PCy3 (6)], whereas in THF species believed to be either square pyramidal [Ru(acac)2L], with apical L, or the corresponding THF adducts, can be detected by 31P NMR spectroscopy. Complexes 3-6 react with CO (1 bar) giving trans-[Ru(acac)2(CO)(L)] [L = PiPr3 (trans-8), PCy3 (trans-9)], which are converted irreversibly into the cis-isomers in refluxing benzene. Complex 5 scavenges traces of dinitrogen from industrial grade dihydrogen giving a bridging dinitrogen complex, cis-[{Ru(acac)2(PiPr3)} 2(μ-N2)] (10). The structures of cis-3, trans-4, 5, 6 and 10 · C6H14 have been determined by single-crystal X-ray diffraction. Complexes trans- and cis-3, 5, 6, cis-8, and trans- and cis-9 each show fully reversible one-electron oxidation by cyclic voltammetry in CH2Cl2 at −50 °C with E1/2(Ru3+/2+) values spanning −0.14 to +0.92 V (versus Ag/AgCl), whereas for the vinylidene complexes [Ru(acac)2 (CCHR)(PiPr3)] [R = SiMe3 (11), Ph (12)] the process is irreversible at potentials of +0.75 and +0.62 V, respectively. The trend in potentials reflects the order of expected π-acceptor ability of the ligands: PiPr3, PCy3 <C 2H4 < CCHR < CO. The UV-Vis spectrum of the thermally unstable, electrogenerated RuIII-ethene cation 6+ has been observed at −50 °C. Cyclic voltammetry of the μ-dinitrogen complex 10 shows two, fully reversible processes in CH2Cl2 at −50 °C at +0.30 and +0.90 V (versus Ag/AgCl) corresponding to the formation of 10+ (RuII,III) and 102+ (RuIII,III). The former, generated electrochemically at −50 °C, shows a band in the near IR at ca. 8900 cm−1 (w1/2 ca. 3700 cm−1) consistent with the presence of a valence delocalized system. The comproportionation constant for the equilibrium 10 + 102+ ? 2 10+ at 223 K is estimated as 1013.6. 相似文献
9.
Richard L. Keiter Ping Ye John William Benson Douglas E. Brandt Arnold L. Rheingold Kraig A. Wheeler 《Inorganica chimica acta》2010,364(1):176-184
The linkage isomers, (OC)5M[κ1-PPh2 CH2CH(PPh2)2] 1 and (OC)5M[κ1-PPh2 CH(PPh2)CH2PPh2] 2 (M = Cr, Mo and W) exist in equilibrium at room temperature. Equilibrium constants for 1Cr ? 2Cr, 1Mo ? 2Mo and 1W ? 2W at 25 °C in CDCl3 are 2.61, 5.0 and 4.74, respectively. Enthalpy favors the forward reaction (ΔH = −13.5, −12 and −12.2 kJ mol−1, respectively) while entropy favors the reverse reaction (ΔS = −37.6, −28 and −28.2 J K−1 mol−1, respectively). Isomerization is much faster than chelation with 1Mo ? 2Mo ? 1W ? 2W > 1Cr ? 2Cr. Enthalpies of activation for 1Cr ? 2Cr and 1W ? 2W are 119.0 and 92.6 kJ mol−1, respectively, and entropies of activation are 1.4 and −28.2 J K−1 mol−1, respectively. Isomerization is 104 times faster for these complexes than for (OC)5M[κ1-PPh2CH2CH2P(p-tolyl)2]. A novel mechanism is proposed to account for the rate differences. The X-ray crystal structure of 2W shows that the phosphorus atom of the short phosphine arm lies very close to a carbon atom of the W(CO)4 equatorial plane (3.40 Å) which could allow “through-space” coupling, accounting in part for the observation of long-range JPC and JPW coupling. The X-ray structure of (OC)5W[κ1-PPh2 C(CH2)PPh2] 5W has been determined for comparison to 2W. 相似文献
10.
Silvia Melnic Charles Simmons Tatiana Chiriac Valeriu Rudic 《Inorganica chimica acta》2011,373(1):167-172
New trinuclear iron(III) furoates with the general formula [Fe3O(α-fur)6(R-OH)3]X, where α-fur C4H3OCOO, R = CH3 (1), C2H5 (2), n-C3H7 (3), n-C4H9 (4), X = NO3− (1-4); [Fe3O(α-Fur)6(DMF)(CH3OH)2]NO3 (5); [Fe3O(α-Fur)6(H2O)(CH3OH)2]Cl (6); [Fe2MO(α-Fur)6(L)(H2O)2], where L = THF (7-9), DMF (10-12), M = Mn2+ (7, 10), Co2+ (8, 11), Ni2+ (9, 12) and [Fe2MO(α-Fur)6(3Cl-Py)3], where M = Mn2+ (13), Co2+ (14), Ni2+ (15); have been prepared and investigated by Mössbauer and IR spectroscopy. The X-ray crystal structure for the 1·2CH3OH complex indicates that it crystallizes in the monoclinic crystal system (P21/n) and has a structure typical of μ3-O-bridged trinuclear iron(III) compounds. Coordination compounds 1, 4, 7, 8 can be used as regulators of the biochemical composition of cyanobacterium Spirulina platensis biomass. The supplementation of these compounds, in concentrations exceeding 5-10 mg/l, increases the content of iron, amino acids, peptides and carbohydrates in Spirulina. 相似文献
11.
Yasuo Nakabayashi Hiroyuki Inada Yuki Minoura Nobuaki Iwamoto Osamu Yamauchi 《Inorganica chimica acta》2009,362(3):869-4841
For reactions of [{RuCl(bpy)2}2(μ-BL)]2+ (bpy = 2,2′-bipyridine, BL = H2N(CH2)nNH2 (n = 4-8, 12), [Ru2-BL]2+) with mononucleotides, the MLCT absorption bands of [Ru2-BL]2+ blue-shifted with hyperchromism for GMP and hypochromism for TMP with time. Reactions of [Ru2-BL]2+ with GMP or TMP proceed via initial Cl− ions replacement by coordination to N7 of GMP and N3 of TMP, respectively. In competition binding experiments for [Ru2-BL]2+ with GMP versus TMP, only GMP selectively coordinated to ruthenium(II). For reactions with calf thymus (CT) DNA, [Ru2-BL]2+ complexes selectively bind to guanine residues of DNA. The higher degrees of binding of [Ru2-BL]2+ to CT-DNA were observed with increasing n values for H2N(CH2)nNH2, which may be explained by the length of the bridging ligands. Studies on the inhibition of the restriction enzyme Acc I revealed that [Ru2-BL]2+ complexes appear to be covalently favorable for the type of difunctional binding. In addition, it is very interesting to observe that circular dichroism spectroscopy of the supernatants obtained following the reactions of CT-DNA with racemic [Ru2-BL]2+ show enrichments of the solutions in the ΔΔ isomers, demonstrating preferences of the ΛΛ isomers for covalent binding to CT-DNA. 相似文献
12.
Jin-Kui TangShu Feng Si En-Qing GaoDai-Zheng Liao Zong-Hui JiangShi-Ping Yan 《Inorganica chimica acta》2002,332(1):146-152
Three novel oxamido-bridged heterobinuclear copper(II)-nickel(II) complexes derived from macrocylic oxamido compound with diamines and tetraazacyclam as blocking ligands were synthesized and characterized by IR, ESR and electronic spectra. Their formula is [Cu(L)Ni(en)2](ClO4)2·0.5C2H5OH·H2O (1), [Cu(L)Ni(tmd)2](ClO4)2·4H2O (2) and [Cu(L)Ni(rac-cth)](ClO4)2·CH3OH (3), where L=1,4,8,11-tetraazacyclotradecanne-2,3-dione, en=1,2-diaminoethande, tmd=1,3-diaminopropane and rac-cth is rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. The crystal structures of the three complexes have been determined. The structures consist of binuclear units in which the copper(II) ion is in a square-planar environment and linked to the nickel(II) ion via the exo-cis oxygen atoms of the oxamido macrocyclic ligand, with Cu?Ni separations of 5.311 (1), 5.420 (2) and 5.307 Å (3), respectively. The temperature dependence of the magnetic susceptibility for 1, 2 and 3 was analyzed by means of the Hamiltonian ?=−2J?Ni?Cu, leading to J=−52.8, −45.7 and −56.9 cm−1 for 1, 2 and 3, respectively. 相似文献
13.
Syntheses of three new N-arylanilido-arylimine bidentate Schiff base type ligand precursors, ortho-C6H4[NH(2,6-iPr2C6H3)](CHNAr1) [Ar1 = p-FC6H4 (2a); C6H5 (2b); p-OMeC6H4 (2c)], and their four-coordinated boron complexes, ortho-C6H4[N(2,6-iPr2C6H3)](CHNAr1)BF2 [Ar1 = p-FC6H4 (3a); C6H5 (3b); p-OMeC6H4 (3c)] are described. The boron complexes 3a-3c were synthesized from the reaction of BF3(OEt2) with the lithium salt of their corresponding ligand. All complexes were characterized by 1H and 13C NMR spectroscopy and molecular structures of complexes 3a and 3c were determined by X-ray crystallography. The photophysical properties of complexes 3a-3c were briefly examined. All three complexes display bright green fluorescence in solution and in the solid state. Electroluminescent devices with complex 3c as the emitter were fabricated. These devices were found to give green emission with maximum current efficiency of 2.92 cd/A and maximum luminance of 670 cd/m2. 相似文献
14.
Tobias Rüffer Björn Bräuer Bernhard Walfort Annie K. Powell Lorenzo Sorace 《Inorganica chimica acta》2007,360(12):3777-3784
The new mononuclear bis(oxamato) complex [n-Bu4N]2[Cu(obbo)] (1) (obbo=o-benzyl-bis(oxamato)) has been synthesized as a precursor for trinuclear oxamato-bridged transition metal complexes. Starting from 1 the homotrinuclear complexes [Cu3(obbo)(pmdta)2(NO3)](NO3)·CH2Cl2·H2O (2) and [Cu3(obbo)(tmeda)2(NO3)2(dmf)] (3) have been prepared, where pmdta = N,N,N′,N″,N″-pentamethyldiethylenetriamine, tmeda = N,N,N′,N′-tetramethylethylenediamine and dmf = dimethylformamide. The crystal structures of 1-3 were solved. The magnetic properties of 2 and 3 were studied by susceptibility measurements versus temperature. For the intramolecular J parameter values of −111 cm−1 (2) and −363 cm−1 (3) were obtained. 相似文献
15.
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
16.
Rampal Pandey Prashant Kumar Sanjay Kumar Singh Daya Shankar Pandey 《Inorganica chimica acta》2011,376(1):195-206
The synthesis and characterization of novel coordination polymers [Co(HCCB)(H2O)2]n (1), [Zn(HCCB)(H2O)2]n (2), {[Cd(HCCB)2]·0.5[Cd(μ-H2O)(H2O)4]2}n (3) and [Cu(HCCB)(H2O)2]n (4) based on 3-(carboxymethylamino)-4-chlorobenzoic acid (H3CCB) and mononuclear complexes [Cu(HBCCB)(H2O)]·H2O (5), [Co(HBCCB)(H2O)]·H2O (6), [Zn(HBCCB)(H2O)] (7) and [Cd(HBCCB)(H2O)] (8) containing 3-bis(carboxymethylamino)-4-chlorobenzoic acid (H3BCCB) have been described. The compounds under investigation have been characterized by elemental analyses, spectral studies and structures of 1-3 and 5 determined crystallographically. Structural data of 1 and 2 revealed that the deprotonated HCCB2− bridges metal centers leading to a double stranded 1D chain. On the other hand, the HCCB2− coordinated thorough carboxylate oxygen and amino nitrogen in 3 to afford a 1D chain whose charge neutrality is maintained by inclusion of aqua-bridged dimer [{Cd(μ-H2O)(H2O)4}2]4+. Strong Cu?Cl interaction (2.754 Å) in 5 imposes a coordination geometry that is half-way between the square planar and square pyramidal. The H3CCB, H3BCCB and 1-3 and 5 are fluorescent at rt. Thermal studies (TG and DSC) on 1-3 suggested higher stability of 2 relative to 1 and 3 [ΔHf (kcal/mol), ΔSf = 152.17, 0.60, 1; 195.56: 0.86, 2; 69.33:0.36, 3]. 相似文献
17.
Luís G. Alves Inês Matos Rui F. Munhá Anabela C. Fernandes Ana M. Martins 《Inorganica chimica acta》2010,363(8):1823-12
Compounds of general formula [(∗Bn2Cyclam)ZrCl2] (∗Bn = 4-tBuC6H4CH2, (4) and 4-CF3C6H4CH2, (5)) were synthesised using Zr(CH2SiMe3)2Cl2(Et2O)2 and the corresponding ligand precursors 1,8-(4-tbutylbenzyl)-1,4,8,11-tetraazacyclotetradecane (H2(4-tBuBn)2Cyclam), (4a), and 1,8-(4-trifluoromethylbenzyl)-1,4,8,11-tetraazacyclotetradecane (H2(4-CF3Bn)2Cyclam), (5a). Complexes 4 and 5, in addition to other [(∗Bn2Cyclam)ZrCl2] compounds previously described by some of us (∗Bn = PhCH2, (1), 3,5-Me2C6H3CH2, (2) and 3,5-tBu2C6H3CH2, (3)) were tested in the polymerization of ethylene in the presence of MAO. System 4/MAO presents the highest activity (2790 g PE molZr−1 h−1 atm−1). The polymers formed are slight to moderately branched polyethylenes with a percentage of branching ranging between 1.2% and 3.3%. The melting points obtained by differential scanning calorimetry (DSC) ranging from 128 to 140 °C, are consistent with rather high average molecular weight polymers with crystallinity close to 50%. 相似文献
18.
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
19.
Three novel cadmium(II) complexes [Cd2(tbpo)(O2CC6H4-p-NO2)2]ClO4·3CH3OH (1) [Cd2(bbap)(O2CC6H4-p-NO2)2]ClO4·4.5CH3OH·0.75H2O (2) and [Cd(ntb)(O2CC6H4-p-NO2)]ClO4·4CH3OH (3) have been synthesized and characterized by IR, elemental analysis, 1H NMR and X-ray crystallography, where tbpo− and bbap− are anions of N,N,N′,N′-tetrakis(2-benzimidazolylmethyl)-2-hydroxo-1,3-diaminopropane and 2,6-bis[bis(2-benzimidazolylmethyl)aminomethyl]-4-methylphenol, respectively; ntb is tris(2-benzimidazolymethyl)amine. Complexes 1 and 2 contain μ-phenolate-bridged and μ-alkoxo-bridged dicadmium(II) cores with the Cd1?Cd2 separation of 3.671 Å for complex 1 and 3.718 Å for 2. One of the 4-nitrobenzoate anions bridged the two cadmium(II) ions in syn-anti mode through its carboxylate group, the other 4-nitrobenzoate is only coordinated with Cd2 in bidentate chelating mode. The two central cadmium(II) atoms are in trigonal bipyramidal and pentagonal bipyramidal geometry. In complex 3, the cadmium(II) atom is coordinated with four nitrogen atoms of ntb and one carboxylate oxygen atom of 4-nitrobenzoate in distorted trigonal bipyramidal geometry. Experiment shows that there is a higher affinity of 4-nitrobenzoate anion as coligand with the dinuclear [Cd2(tbpo)]3+ and [Cd2(bbap)]3+ cores than that with the mononuclear [Cd(ntb)]2+ core. 相似文献
20.
Crestina S. Consorti 《Inorganica chimica acta》2006,359(15):4874-4884
Reactions of the diphosphine H2P(CH2)5PH2 and fluorous alkenes H2CCHRfn (excess; Rfn = (CF2)n−1CF3; n = a, 6; b, 8; c, 10) at 60 °C in the presence of AIBN give the precursors (RfnCH2CH2)2P(CH2)5P(CH2CH2Rfn)2 (2a-c; 68-74%). These react with Pd(O2CCF3)2 in CF3C6F5 at 80 °C to give the title complexes (5a-c, 51-18%). Addition of LiCl to 5b gives (6b, 97%); subsequent reaction with MeLi affords the corresponding methyl complex (97%). A solvate of 6b is crystallographically characterized. The structure exhibits CH2CH2Rf8 groups with nearly anti C-C-C-C conformations, extending in parallel above and below the palladium square plane to create fluorous lattice domains. Reactions of 2b and other metal complexes are described; in the cases of (PhCN)2PdCl2 or (COD)2PtCl2 (CF3C6H5, room temperature), bimetallic species in which two MCl2 moieties are bridged by two diphosphines appear to form. The CF3C6F11/toluene partition coefficients of 2a-c and 5a-c establish high fluorophilicities; despite the lower fluorine weight%, those of 5a-c are slightly greater ((97.4-99.7):(2.6-0.3) versus (95.3-99.3):(4.7-0.7)). 相似文献