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1.
《Inorganica chimica acta》2006,359(9):2896-2909
[RuCl3(NO)(P–P)], [P–P = R2P(CH2)nPR2 (n = 1–3) and R2P(CH2)POR2, PR2–CHCH–PR2, R = Ph and (C6H11)2P-(CH2)2-P(C6H11)2] were obtained and characterized by 31P {1H} NMR, IR spectroscopies and cyclic voltammetry. The structures of fac-[RuCl3(NO)(P–P)], P–P = dppm (1), dppe (2), c-dppen (3) and dppp (4), mer-[RuCl3(NO)(dcpe)] (6a) and mer-[RuCl3(NO)(dppmO)] (7) have been determined by X-ray diffraction. Photochemical isomerization of fac- to mer-[RuCl3(NO)(P–P)] was observed under white light in a CH2Cl2 solution and in solid state. The isomerization processes were followed by IR and 31P {1H} spectra. The mer-[RuCl3(15NO)(dppb)] isomer was used for the definition of the phosphorus atoms in the structure of the complex in solution. The electrochemical study shows that the oxidation/reduction processes observed in these complexes are dependent on both the isomer (fac or mer) and the solvent. In CH2Cl2, the NO+ reduction potentials are less negative for the mer-isomers than for the fac ones, while in CH3CN solvent these potentials are, in general, very close for both isomers. 相似文献
2.
Diphosphine-bridged dimers of oxo-centered triruthenium-acetate cluster units, i.e., [{Ru3O(OAc)6(py)2}2(dppan)](PF6)2 (2) and [{Ru3O(OAc)6(py)2}2(dppf)](PF6)2 (3) were prepared by reaction of 2.3 equivalent [Ru3O(OAc)6(py)2(CH3OH)](PF6) with 9,10-bis(diphenylphosphino)anthracene (dppan) or 1,1′-bis(diphenylphosphino)ferrocene (dppf), respectively. Apparent redox wave splitting is observed in complex 2, revealing the presence of electronic communication between two triruthenium units mediated through bridging dppan. The complexes were characterized by elemental analysis, IR, UV-Vis, 31P NMR, and ES-MS spectroscopies, and cyclic and differential-pulse voltammetry. The crystal structure of complex 3 was determined by X-ray crystallography. 相似文献
3.
《Inorganica chimica acta》2006,359(5):1513-1518
[ReOX3(PPh3)2] complexes (X = Cl and Br) react with equivalent amounts of 2-hydroxypyridine (Hhp) under formation of the mono-substituted, zwitterionic complexes mer-[ReOCl3(Hhp)(PPh3)] (1) and mer-[ReOBr3(Hhp)(PPh3)] (2). Crystal structure determinations of 1 · CH2Cl2 and 2 revealed the Cl and Br ligands adopt a mer arrangement. The Hhp ligands coordinate neutral and monodentate via their exocyclic oxygen atoms in axial positions, trans to the oxo groups. The distorted octahedral coordination sphere of the rhenium(V) complexes is completed by the phosphorus atom of the remaining PPh3 ligand. 相似文献
4.
《Inorganica chimica acta》2006,359(5):1573-1581
From the 2,4-bis(cyanamido)cyclobutane-1,3-dione dianion (2,4-NCNsq2−), two copper complexes [Cu2(PPh3)4(PhCN)2(μ-2,4-NCNsq)] · PhCN (1) and [Cu(dien)(μ-2,4-NCNsq) · H2O]n (2) have been synthesized and characterized by IR and electronic absorption spectroscopies. Their structures have been determined by X-ray crystallography. Complex 1 is a dinuclear copper(I) compound with a 2,4-NCNsq2− ligand bridging two copper atoms through the nitrile nitrogen atoms. Complex 2 appears as a 3D network constituted of copper(II) atoms bridged by 2,4-NCNsq2− dianions. This complex presents an unexpected coordination mode of the bis(cyanamido) ligands which are both coordinated via the nitrile functions and via the amido nitrogen atoms of the NCN groups. 相似文献
5.
Fabrice Pointillart Kevin Bernot Jeremy Colas Lorenzo Sorace Roberta Sessoli 《Inorganica chimica acta》2008,361(12-13):3427-3431
The reaction of [Ru(salen)(PPh3)Cl] and the 5-imidazol-substituted nitronyl nitroxide radical (NIT-(5)ImH) yields the [Ru(salen)(PPh3)(NIT-(5)ImH)](ClO4) (1) complex which has been characterized by single crystal X-ray diffraction. This analysis reveals that the Ru(III) ion is coordinated to a tetradentate salen2? ligand in equatorial positions while one PPh3 ligand and one NIT-(5)ImH radical are coordinated in axial positions. This led to RuIII ions in tetragonally elongated octahedral geometry. From the magnetic point of view ferromagnetic intramolecular interaction (J1 = +2.47 cm?1) have been found between the Ru(III) ion and the coordinated NIT-(5)ImH while no significant intermolecular antiferromagnetic interactions are observed at low temperature leading to a ground spin state S = 1. The absence of intermolecular magnetic interaction is explained by considering the crystal packing of (1) where the [Ru(salen)(PPh3)(NIT-(5)ImH)]+ moieties are relatively well isolated. This has to be compared with the situation observed in the previously reported [Ru(salen)(PPh3)-(NIT)]+ compound (2) where ferromagnetic RuIII–NIT interaction were identified and the crystal packing generate intermolecular antiferromagnetic interactions that complicated the study. The analysis of this compound confirms the rather isotropic g values that were found of (2) and of [Ru(salen)(PPh3)(N3)], (3) a radical-free analogue. Moreover it is also a step towards extended structures based on RuIII–NIT moieties since this compound possesses a free bischelating site likely to coordinate additional metallic ions. 相似文献
6.
Richard V. Macri Janka Karlovská Gustavo F. Doncel Xiaosong Du Bhadreshkumar B. Maisuria André A. Williams Eko W. Sugandhi Joseph O. Falkinham Alan R. Esker Richard D. Gandour 《Bioorganic & medicinal chemistry》2009,17(8):3162-3168
Three series of homologous dendritic amphiphiles—RCONHC(CH2CH2COOH)3, 1(n); ROCONHC(CH2CH2COOH)3, 2(n); RNHCONHC(CH2CH2COOH)3, 3(n), where R = n-CnH2n+1 and n = 13–22 carbon atoms—were assayed for their potential to serve as antimicrobial components in a topical vaginal formulation. Comparing epithelial cytotoxicities to the ability of these homologues to inhibit HIV, Neisseria gonorrhoeae, and Candida albicans provided a measure of their prophylactic/therapeutic potential. Measurements of the ability to inhibit Lactobacillus plantarum, a beneficial bacterium in the vagina, and critical micelle concentrations (CMCs), an indicator of the potential detergency of these amphiphiles, provided additional assessments of safety. Several amphiphiles from each homologous series had modest anti-HIV activity (EC50 = 110–130 μM). Amphiphile 2(18) had the best anti-Neisseria activity (MIC = 65 μM), while 1(19) and 1(21) had MICs against C. albicans of 16 and 7.7 μM, respectively. Two measures of safety showed promise as all compounds had relatively low cytotoxic activity (EC50 = 210–940 μM) against epithelial cells and low activity against L. plantarum, 1(n), 2(n), and 3(n) had MICs ? 490, 1300, and 940 μM, respectively. CMCs measured in aqueous triethanolamine and in aqueous potassium hydroxide showed linear dependences on chain length. As expected, the longest chain in each series had the lowest CMC—in triethanolamine: 1(21), 1500 μM; 2(22), 320 μM; 3(22), 340 μM, and in potassium hydroxide: 1(21), 130 μM; 3(22), 40 μM. The CMC in triethanolamine adjusted to pH 7.4 was 400 μM for 1(21) and 3900 μM for 3(16). The promising antifungal activity, low activity against L. plantarum, relatively high CMCs, and modest epithelial cytotoxicity in addition to their anti-Neisseria properties warrant further design studies with dendritic amphiphiles to improve their safety indices to produce suitable candidates for antimicrobial vaginal products. 相似文献
7.
《Inorganica chimica acta》2006,359(11):3617-3624
8.
Syntheses and crystal structures of di- and trimethyltin (IV) derivatives with phenylphosphonic acid
Three types of methyltin phosphonates, {[(CH3)3Sn]4(O3PPh)2}n (1), {[(CH3)3Sn]2(O3PPh) · CH3OH}n (2) and {[(CH3)2SnO3PPh]4}n (3) were synthesized by the reaction of phenylphonic acid with trimethyltin (IV) chloride and dimethyltin (IV) dichloride, respectively. Complexes 1, 2 and 3 were characterized by elemental analysis, IR, NMR (1H, 13C, 31P and 119Sn) spectroscopy, TGA and X-ray crystallography diffraction analysis. The X-ray analysis of complex 1 shows that the structure is a polymeric infinite 1D zigzag chain. In complex 2, the oxygen atom of methanol molecule is coordinated to the tin atoms, and a 2D network is generated via O–H?O hydrogen bonds. In complex 3, a novel 2D network containing 12-membered (Sn3O6P3) rings is formed. 相似文献
9.
《Inorganica chimica acta》2006,359(5):1549-1558
Reactions of Cp*RhCl2(PPh3) (1) with 1-alkyne and H2O in the presence of KPF6 generated alkenyl ketone complexes [Cp*Rh(CRCHCOCH2R)(PPh3)](PF6) (2) (R = Ph (a), C6H4−p-Me (b), C6H4-p-COOMe (c), C6H4-p-NO2 (d)). A similar complex [Cp*Rh(CPhCHCOCH2Ph)(PMePh2)](PF6) (2e) was obtained by use of Cp*RhCl2(PMePh2). It was revealed by X-ray analyses of 2b, 2c and 2e that the complexes 2 consist of the five-membered ring structures bound by the carbon and oxygen atoms of the alkenyl ketone group. Similar reactions of Cp*IrCl2(PPh3) (6) or (C6Me6)RuCl2(PPh3) (7) proceeded with a cleavage of C–C triple bond of 1-alkyne without formation of an alkenyl ketone complex, affording the corresponding carbonyl complexes, [Cp*IrCl(PPh3)(CO)](PF6) (8) or [(C6Me6)RuCl(PPh3)(CO)](PF6) (9). The diphosphine complexes [(Cp*MCl2)2{μ-diphos}] (4: M = Rh, diphos = dppm,; 12a: M = Ir, diphos = dppm; 12b: M = Ir, diphos = dppb) gave a Cl-bridged rhodium complex [{Cp*Rh(μ-Cl)}2{μ-dppm}](PF6)2 (5), mono-carbonyl or dicarbonyl iridium complexes,[(Cp*IrCl2){μ-dppm}{Cp*IrCl(CO)}](PF6)(13a) or [{Cp*IrCl(CO)}2{μ-dppb}](PF6)2 (14b), respectively. 相似文献
10.
《Inorganica chimica acta》2006,359(4):1041-1049
Five new complexes of the type [Co(CNC6H3iPr2-2,6)4PPh2-R′-PPh2]X, X = BF4, ClO4; R′ =–(CH2)2– (1), –(CH2)3– (2), –CHCH-trans (3), –CC– (4) and –C6H4-p (5); and two new bimetallic complexes, [{Co(CNC6H3iPr2-2,6)4}2(μ-PPh2(CH2)3PPh2)](ClO4)2 (6) and [{Co(CNC6H3iPr2-2,6)4}2(μ-PPh2C6H4PPh2-p)](ClO4)2 (7), have been synthesized and characterized by various spectroscopic methods.Known monometallic and bimetallic complexes bearing the ligand CNC6H3Et2-2,6 instead of CNC6H3iPr2-2,6 have been included in the 31P NMR, cyclic voltammetric and mass spectrometry studies.Comparison of the CNC6H3iPr2-2,6 with the CNC6H3Et2-2,6 complexes shows that the increased steric bulkiness of the former makes it more suitable for synthesis of the monometallic complexes, whilst the CNC6H3Et2-2,6 is more apt to give bimetallic complexes.Thus, the two arylisocyanides are complementary with respect to synthesis of the monometallic and bimetallic complexes.The 31P NMR indicates that the diphosphines in monometallic complexes behave as non-fluxional, monodentate ligands at ambient temperature, with 31P–31P coupling shown for the PPh2CH2PPh2, PPh2(CH2)2PPh2 and PPh2CCPPh2 ligands. Cyclic voltammetry fails to show electronic communication in the bimetallic complexes, and mass spectrometry indicates significantly greater stability for fragments containing potentially chelating diphosphines as compared to diphosphines that cannot chelate. 相似文献
11.
《Inorganica chimica acta》2006,359(9):2835-2841
Rh(I) carbene complexes of [RhX(bmim)(η4-1,5-cod)] type (bmim = 1-butyl-3-methyl imidazolium cation, X = Cl 2, Br 3, I 4), obtained in the reaction of [Rh(OMe)(η4-1,5-cod)]2 (1) with [bmim]X ionic liquids, catalyzed polymerization of phenylacetylene (PA) to cis-polyphenylacetylene (PPA) in CH2Cl2 and in ionic liquids. The yield of PPA increased and molecular weight (Mw) decreased after addition of phosphorus ligands PPh3 or P(OPh)3. Complex 4 reacted with P(OPh)3 giving cis-[RhI(bmim)(P(OPh)3)2] (5) complex which catalyzed oligomerization but not polymerization of PA. 相似文献
12.
Barbara Modec 《Inorganica chimica acta》2008,361(9-10):2863-2870
A series of acetato complexes of molybdenum(V), based on the singly metal–metal bonded {Mo2O4}2+ structural fragment, has been prepared. A dinuclear (PyH)3[Mo2O4Cl4(OOCCH3)] · CH3CN (1) (PyH+ = pyridinium cation, C5H5NH+) was obtained upon the reaction of (PyH)5[MoOCl4(H2O)]3Cl2 with the equimolar solution of pyridine and acetic acid in acetonitrile at ambient conditions. The acetato ligand in 1 is coordinated to a pair of molybdenum atoms in a syn–syn bidentate bridging manner. (PyH)n[MoOBr4]n afforded in an analogous synthetic procedure a tetranuclear cluster, [Mo4O8(OOCCH3)3(OH)Py4] · 1/2CH 3CN · 1/2H2O (3), with a novel core which may be envisioned as the acetate- and hydroxide-assisted assembly of {Mo2O4}2+ building blocks. Its structure is presented in terms of known tetranuclear clusters which are also composed of two {Mo2O4}2+ units. The acetato ligands in 3 adopted apart from bidentate bridging binding modes also a monodentate one. Partial substitution of chlorido ligands in (PyH)3[Mo2O4Cl4(OOCCH3)] · CH3CN (1) with pyridine resulted in a neutral [Mo2O4Cl(OOCCH3)Py3] · PriOH · Py (2) which retained the original acetate coordination. The title compounds were fully characterized by X-ray diffraction studies and infrared vibrational spectroscopy. 相似文献
13.
Qing-Xiang Liu Xiao-Jun Zhao Xiu-Mei Wu Li-Na Yin Jian-Hua Guo Xiu-Guang Wang Jin-Cheng Feng 《Inorganica chimica acta》2008,361(9-10):2616-2622
The precursors bis[N-(alkyl)benzimidazoliumylmethyl]durene halide (1a: alkyl = C2H5, halide = Br?; 1b: alkyl = n-C4H9, halide = Cl?; durene = 1,2,4,5-tetramethylbenzene) and their two new NHC silver(I) complexes [Durene(CH2BimyEtAgBr)2] (2a) and [Durene(CH2BimynBuAgCl)2] (2b) (Bimy = benzimidazol-2-ylidene) have been prepared and characterized. In the crystal structures of 2a and 2b the aromatic π–π stacking interactions are observed. 相似文献
14.
《Inorganica chimica acta》2006,359(7):2241-2245
The reaction of N-benzesulfonyl-l-glutamic acid (Bs-glu) with Zn(CH3COO)2 · 2H2O or Co(CH3COO)2 · 4H2O in the presence of imidazole (Im) produced two novel complexes [Zn(Im)2(Bs-glu)]n (1) and [Co(Im)2(Bs-glu)]n (2). Both of the complexes exhibit similar one-dimensional structural motif and coordination environment. Bs-glu adopts the bis-monodentated coordination mode linking two adjacent metal ions. The complex 1 shows intense photoluminescence in the solid state. Magnetic measurements for 2 show that the exchange interaction of the two Co(II) ions is antiferromagnetic. 相似文献
15.
《Bioorganic & medicinal chemistry》2016,24(2):270-276
A series of new cobalt(III) complexes were prepared. They are [CoL1(py)3]·NO3 (1), [CoL2(bipy)(N3)]·CH3OH (2), [CoL3(HL3)(N3)]·NO3 (3), and [CoL4(MeOH)(N3)] (4), where L1, L2, L3 and L4 are the deprotonated form of N′-(2-hydroxy-5-methoxybenzylidene)-3-methylbenzohydrazide, N′-(2-hydroxybenzylidene)-3-hydroxylbenzohydrazide, 2-[(2-dimethylaminoethylimino)methyl]-4-methylphenol, and N,N′-bis(5-methylsalicylidene)-o-phenylenediamine, respectively, py is pyridine, and bipy is 2,2′-bipyridine. The complexes were characterized by infrared and UV–Vis spectra, and single crystal X-ray diffraction. The Co atoms in the complexes are in octahedral coordination. Complexes 1 and 4 show effective urease inhibitory activities, with IC50 values of 4.27 and 0.35 μmol L−1, respectively. Complex 2 has medium activity against urease, with IC50 value of 68.7 μmol L−1. While complex 3 has no activity against urease. Molecular docking study of the complexes with Helicobacter pylori urease was performed. 相似文献
16.
Jae-Hyuk Her Bretni S. Kennon William W. Shum Peter W. Stephens Joel S. Miller 《Inorganica chimica acta》2008,361(12-13):3462-3464
LnIII[Ru2(CO3)4] · 8H2O (Ln = Gd, Nd, Ho, Yb) is formed from the reaction of LnIII and [Ru2(CO3)4]3? in water. These LnIII materials have a 3D network structure composed of linked chains and μn-CO3 linkages to both Ru and LnIII sites, and are best described as LnIII(OH2)4[Ru2(CO3)4]1/2[Ru2(CO3)4(OH2)2]1/2 · 3H2O. Complete characterization of the GdIII species is presented, as the other LnIII are isostructural and exhibit large spin–orbit coupling leading to complex magnetic behavior. Magnetic ordering is not observed above 2 K. 相似文献
17.
《Inorganica chimica acta》2006,359(7):2029-2040
Two μ-alkoxo-μ-carboxylato bridged dinuclear copper(II) complexes, [Cu2(L1)(μ-HCO2)] (1) ((H3L1 = 1,3-bis(5-bromosalicylideneamino)-2-propanol)), [Cu2(L2)(μ-HCO2)] · dmf (2) (H3L2 = 1,3-bis(3,5-chlorosalicylideneamino-2-propanol)), and two μ-alkoxo-μ-dicarboxylato doubly bridged tetranuclear copper(II) complexes, [{Cu2(L3)}2(μ-O2C–C(CH3)2–CO2)] · 5H2O · 3CH3OH (3) ((H3L3 = 1,3-bis(salicylid-deneamino)-2-propanol)) and [{Cu2(L3)}2(μ- O2CCH2–C6H4–CH2CO2)] · 2H2O (4) have been prepared and characterized. The single crystal X-ray analysis shows that the structures of complexes 1 and 2 are dimeric with two adjacent copper(II) atoms bridged by μ-alkoxo-μ-carboxylato ligands with the Cu⋯Cu distances and Cu–O(alkoxo)–Cu angles are 3.511 Å and 132.85° for 1, 3.517 Å and 131.7° for 2, respectively. Complexes 3 and 4 consist of μ-alkoxo-μ-dicarboxylato doubly bridged tetranuclear Cu(II) complexes with mean Cu–Cu distances and Cu–O–Cu angles of 3.158 Å and 108.05° for 3 and 3.081 Å and 104.76° for 4, respectively. Magnetic measurements reveal that 1 and 2 are strong antiferromagnetically coupled with 2J = −156 and −152 cm−1, respectively, while 3 and 4 exhibit ferromagnetic coupling with 2J = 86 and 155.2 cm−1, respectively. The 2J values of 1–4 are linearly correlated to the Cu–O–Cu angles. Dependence of the pH at 25 °C on the reaction rate of oxidation of 3,4-di-tert-butylcatechol (3,5-dtbc) to the corresponding quinone catalyzed by 1–4 was studied. Complexes 1–4 exhibit high catecholase-like activity at pH 9.0 and 25 °C for oxidation of 3,5-di-tert-butylcatechol. 相似文献
18.
Lisa Dalla Via Aída N. García-Argáez Arianna Adami Silvia Grancara Pamela Martinis Antonio Toninello Daniela Belli Dell’Amico Luca Labella Simona Samaritani 《Bioorganic & medicinal chemistry》2013,21(22):6965-6972
A convenient synthetic route and the characterization of complexes trans-[PtCl2(L)(PPh3)] (L = Et2NH (2), (PhCH2)2NH (3), (HOCH2CH2)2NH) (4) are reported. The antiproliferative activity was evaluated on three human tumor cell lines. The investigation on the mechanism of action highlighted for the most active complex 4 the capacity to affect mitochondrial functions. In particular, both the induction of the mitochondrial permeability transition phenomenon and an aspecific membrane damage occurred, depending on concentration. 相似文献
19.
《Inorganica chimica acta》2006,359(9):2864-2869
Treatment of 1,3-diphosphinopropane with acetylacetone in the presence of HCl gives the new chiral bis(phosphaadamantyl)propane ligand (bpap) (1) as a mixture of diastereoisomers. Recrystallization from ethanol gives a mixture enriched in rac diastereoisomer (90% rac/10% meso). The enriched mixture reacts with [RuHCl(PPh3)3] in refluxing THF to give [RuHCl(bpap)(PPh3)] (2) in 73% yield. Compound 2 reacts readily with chiral diamines giving octahedral trans-[RuHCl(bpap)(diamine)] complexes 3 (diamine = (1R,2R)-1,2-diaminocyclohexane) and 4 (diamine = (1R,2R)-1,2-diphenylethylenediamine). Compounds 3 and 4 are very active catalysts for H2-hydrogenation of neat acetophenone in the presence of KOtBu as a strong base under mild conditions (room temperature, 3 atm of H2). The low ee values for 1-phenethanol can be attributed to the similar shapes of two terminal adamantoid cages and the flexible backbone of the bpap ligand. The structures of complexes 2 and 3 have been determined by single-crystal X-ray diffraction. 相似文献
20.
Two tetracyanometalate building blocks, [Fe(5,5′-dmbipy)(CN)4]? (2) and [Fe(4,4′-dmbipy)(CN)4]? (3) (5,5′-dmbipy = 5,5′-dimethyl-2,2′-bipyridine; 4,4′-dmbipy = 4,4′-dimethyl-2,2′-bipyridine), and two cyano-bridged heterobimetallic complexes, [Cu2(bpca)2(H2O)2Fe2(5,5′-dmbipy)2(CN)8] · 2[Cu(bpca)Fe(5,5′-dmbipy)(CN)4] · 4H2O (4) and [Cu(bpca)Fe(4,4′-dmbipy)(CN)4]n (5) (bpca = bis(2-pyridylcarbonyl)amidate), have been synthesized and structurally characterized. Complex 4 contains two dinuclear and one tetranuclear heterobimetallic clusters in an asymmetric unit whereas the structure of complex 5 features a one-dimensional heterobimetallic zigzag chain. The Cu(II) ion is penta-coordinated in the form of a distorted square-based pyramid. Magnetic studies show ferromagnetic coupling between Cu(II) and Fe(III) ions with g = 2.28, J1 = 2.64 cm?1, J2 = 5.40 cm?1 and TIP = ?2.36 × 10?3 for complex 4, and g = 2.17, J = 4.82 cm?1 and zJ′ = 0.029 cm?1 for complex 5. 相似文献