共查询到20条相似文献,搜索用时 31 毫秒
1.
The reaction of [C5H4(CH2)nX]Tl (1: n = 2, X = NMe2, OMe, CN; n = 3, X = NMe2) with [(η6-C6H6)RuCl(μ-Cl)]2, 2, afforded the sandwich compounds [{η5-C5H4(CH2)nX}Ru(η6-C6H6)]PF6, 3, and [η5-C5H4(CH2)nX]2Ru, 4. Photolytic cleavage of 3 in acetonitrile afforded the tethered products [{η5:κN-C5H4(CH2)nX}Ru(CH3CN)2]PF6, 5. 相似文献
2.
The reaction of metallocene complexes of the type [η5:C5H4-(CH2)n-C6H5]2MCl2 (n=1-5; M=Zr, Hf) with EtLi gives the mono nuclear ethyl derivatives [η5:C5H4-(CH2)n-C6H5]2M(Et)Cl and the metallacycles [η5:C5H4-(CH2)n-C6H5][η5:C5H4-(CH2)n-η1:C6H4]MEt. A large excess of EtLi affords the dinuclear species [η5:C5H4-(CH2)n-η6:C6H5]2M2Cl2 (n=2-5). All types of complexes can be activated with methylalumoxane (MAO) and then be used for catalytic polymerization of ethylene. 相似文献
3.
Jörg Wagler Erica Brendler Sigrid Goutal Bernhard Kempf Gerhard Roewer 《Inorganica chimica acta》2005,358(14):4270-4286
The reaction between phenyltrichlorosilane and the tetradentate ligands o-HO-C6H4-C(CH3)N-(CH2)n-NC(CH3)-o-C6H4-OH (n = 2, 3, 4), supported by an amine base, yields pentacoordinate silicon complexes (C6H5)Si-[o-O-C6H4-C(CH3)N-(CH2)n-N-C(CH2)-o-C6H4-O] with enamine functionalized ligands. This reaction pattern can be transferred onto various ligands of 2-iminomethylphenolate-type. The resulting pentacoordinate silicon complexes react with a variety of Brønsted acids HY to yield hexacoordinate salen silicon complexes (C6H5)(Y)Si-[o-O-C6H4-C(CH3)N-(CH2)n-NC(CH3)-o-C6H4-O] (Y = benzoate, picrate, 8-oxyquinolinate, 2-oxy-1,4-naphthoquinonate, p-tert-butylphenolate, (5-phenyltetrazol)-2-ide, fluoride, tetrafluoroborate). Hexacoordination of their Si-atoms was confirmed by 29Si NMR spectroscopy and, in some cases, by X-ray crystal structure analysis. Examples for similarities and differences in the coordination behavior of the silicon atom and its heavier congeners (Ge, Sn) in the salen-type coordination sphere as well as data regarding the nucleophilicity of some of these novel enamine complexes are presented. 相似文献
4.
Effect of chain length on the stability of lecithin bilayers 总被引:1,自引:0,他引:1
The shift reagent NaCl3 was added to vesicles of synthetic, saturated (DiC10-C16) lecithins and egg lecithin and the accessibility of the N(CH3)3 groups to Na3+ ions was studied by NMR. Long chain lecithins, e.g. dipalmitoyl and egg lecithin form bilayers “stable” on the time scale of our experiments and practically impermeable to cations. Short chain lecithins on the other hand form short-lived vesicles surrounded by unstable bilayers which are not effective cation barriers. Ion transport across the latter lecithin bilayers may involve, besides passive diffusion, collision-induced transient rupture and resealing of bilayers coupled with ion movement. 相似文献
5.
The equilibrium geometries and electron affinities of the R-SS/R-SS-(R=CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, t-C4H9, n-C5H11) species have been studied using the higher level of the Gaussian-3(G3) theory and 21 carefully calibrated pure and hybrid density functionals (five generalized gradient approximation (GGA) methods, seven hybrid GGAs, three meta GGA methods, and six hybrid meta GGAs) in conjunction with diffuse function augmented double-ζ plus polarization (DZP++) basis sets. The geometries are fully optimized with each method and discussed. The reliable adiabatic electron affinity has been presented by means of the high level of G3 technique. With the DZP++ DFT method, three measures of neutral/anion energy differences reported in this work are the adiabatic electron affinity, the vertical electron affinity, and the vertical detachment energy. The adiabatic electron affinities, obtained at the BP86, M05-2X, B3LYP, M06, B98, M06-2X, mPW1PW91, HCTH, B97-1, M05, PBE1PBE, and VSXC methods, are in agreement with the G3 results. These methods perform better for EA prediction and are considered to be reliable. 相似文献
6.
Angelino Doppiu 《Inorganica chimica acta》2004,357(6):1773-1780
The dimer [Ir(μ-Cl)(C8H14)2]2 reacts with the ligands (S)-(C5H4CH2CH(Ph)PPh2)Li and (R)-(C5H4CH(Cy)CH2PPh2)Li to give (S)-[Ir(η5-C5H4CH2CH(Ph)PPh2-κP)(C8H14)] and (R)-[Ir(η5-C5H4CH(Cy)CH2PPh2-κP)(C8H14)], which upon treatment with CH3I at room temperature afford the cationic iridium(III) compounds (S,SIr)-[Ir(η5-C5H4CH2CH(Ph)PPh2-κP)(CH3)(C8H14)][I] as a single diastereomer, and (R)-[Ir(η5-C5H4CH(Cy)CH2PPh2-κP)(CH3)(C8H14)][I] as a 9:1 mixture of two diastereomers. If the oxidative addition reaction is performed at reflux in methylene chloride, the starting complexes convert to the neutral compounds (S)-[Ir(η5-C5H4CH2CH(Ph)PPh2-κP)(CH3)(I)] and (R)-[Ir(η5-C5H4CH(Cy)CH2PPh2-κP)(CH3)(I)] as 1.6:1 and 3.3:1 mixtures of diastereoisomers, respectively. Carbonyl iridium complexes are synthesized by reacting [IrCl(CO)(PPh3)2] with the ligands to afford (S)-[Ir(η5-C5H4CH2CH(Ph)PPh2-κP)(CO)] and (R)-[Ir(η5-C5H4CH(Cy)CH2PPh2-κP)(CO)]. They give upon treatment with CH3I the cationic species (S)-[Ir(η5-C5H4CH2CH(Ph)PPh2-κP)(CH3)(CO)][I] and (R)-[Ir(η5-C5H4CH(Cy)CH2PPh2-κP)(CH3)(CO)][I] as 1.6:1 and 3:1 mixture of diastereomers, respectively. No migratory-insertion of the methyl group into the carbonyl-metal bond has been observed even after prolonged heating. 相似文献
7.
Chanchai Sattayanon Nawee Kungwan Winita Punyodom Puttinan Meepowpan Siriporn Jungsuttiwong 《Journal of molecular modeling》2013,19(12):5377-5385
A theoretical investigation of the ring-opening polymerization (ROP) mechanism of ε-caprolactone (CL) with tin(II) alkoxide, Sn(OR)2 initiators (R?=?n-C4H9, i-C4H9, t-C4H9, n-C6H13, n-C8H17) was studied. The density functional theory at B3LYP level was used to perform the modeled reactions. A coordination-insertion mechanism was found to occur via two transition states. Starting with a coordination of CL onto tin center led to a nucleophilic addition of the carbonyl group of CL, followed by the exchange of alkoxide ligand. The CL ring opening was completed through classical acyl-oxygen bond cleavage. The reaction barrier heights of ε-caprolactone with different initiators were calculated using potential energy profiles. The reaction of ε-caprolactone with Sn(OR)2 having R?=?n-C4H9 has the least value of barrier height compared to other reactions. The rate constants for each reaction were calculated using the transition state theory with TheRATE program. The rate constants are in good agreement with available experimental data. 相似文献
8.
The long-chain saturated and mono-unsaturated hydrocarbon content of the juice sacs of five mandarin cultivars (Mediterranean, Honey, Wilking, Kinnow, King) were examined. Normal homologues accounted for more than 47% of the saturated and more than 75% of the monoene hydrocarbons. In the saturated fraction the major hydrocarbon was n-C25 but in the monoene fraction n-C25 predominated in Kinnow and King while C29 predominated in Mediterranean, Honey and Wilking. All five cultivars could be differentiated from each other and from other citrus species by their hydrocarbon patterns. The noticeably high normal/iso ratios of saturated C23 and C25 hydrocarbons previously shown to be characteristic of mandarin species, Citrus unshiu and C. reticulata, were also found in C. nobilis and C. deliciosa. 相似文献
9.
William J. Hunks 《Inorganica chimica acta》2006,359(11):3605-3616
The reaction of digold(I) diphosphine complexes [Au2(O2CCF3)2(μ-Ph2P-X-PPh2)] with dithiols HS-Y-SH can give either macrocyclic complexes [Au2(μ-S-Y-S)(μ-Ph2P-X-PPh2)] or polymeric complexes [Au2(μ-S-Y-S)(μ-Ph2P-X-PPh2)]n. The structures of the macrocyclic complex [Au2{μ-(S-4-C6H4)2S}{μ-Ph2P(CH2)4PPh2}], and the polymeric complexes [Aun{μ-(S-CH2CO2CH2CH2O)2-1,4-C6H4}n(μ-trans-Ph2PCHCHPPh2)n] and [Aun{μ-(S-CH2CO2CH2CH2O)2-1,5-C10H6}n(μ-trans-Ph2PCHCHPPh2)n] have been determined. Evidence is presented that the complexes exist primarily as macrocycles in solution and that, in favorable cases, ring-opening polymerization occurs during crystallization. 相似文献
10.
The optimized geometries, electron affinities, and dissociation energies of the alkylthio radicals have been determined with the higher level of the Gaussian-3(G3) theory. The geometries are fully optimized and discussed. The reliable adiabatic electron affinities with ZPVE correction have been predicted to be 1.860 eV for the methylthio radical, 1.960 eV for the ethylthio radical, 1.980 and 2.074 eV for the two isomers (n-C3H7S and i-C3H7S) of the propylthio radical, 1.991, 2.133 and 2.013 eV for the three isomers (n-C4H9S, t-C4H9S, and i-C4H9S) of the butylthio radical, and 1.999, 2.147, 2.164, and 2.059 eV for the four isomers (n-C5H11S, b-C5H11S, c-C5H11S, and d-C5H11S) of the pentylthio radical, respectively. These corrected EAad values for the alkylthio radicals are in good agreement with available experiments, and the average absolute error of the G3 method is 0.041 eV. The dissociation energies of S atom from neutral CnH2n+1S (n?=?1–5) and S- from corresponding anions CnH2n+1S- species have also been estimated respectively to examine their relative stabilities. 相似文献
11.
《生物化学与生物物理学报:生物膜》1987,903(3):465-472
The interaction of synthetic peptides corresponding to the signal sequences of Escherichia coli alkaline phosphatase: Lys-Gln-Ser-Thr-Ile-Ala-Leu-Ala-Leu-Leu-Pro-Leu-Leu-Phe-Thr-Pro-Val-Thr-Lys-Ala-OCH3, chicken lysozyme: Met-Lys-Ser-Leu-Leu-Ile-Leu-Val-Leu-Cys(Bzl)-Phe-Leu-Pro-Leu-Ala-Ala-Leu-Gly-OCH2-C6H5 and variant of the chicken lysozyme signal sequence with a charged residue in the hydrophobic region: Lys-Leu-Leu-Ile-Ala-Leu-Val-Leu-Lys-Phe-Leu-Pro-Leu-Ala-Ala-Leu-Gly-OCH3 with model membranes of brain phosphatidylserine (PS) and egg phosphatidylcholine (PC) have been investigated by 90° light scattering and fluorescence spectroscopy. Our results indicate that the association of signal peptides with model membranes results in extensive perturbation of the lipid bilayer so as to cause fusion of PS vesicles and aggregation of PC vesicles. The vesicles are also rendered permeable to hydrophilic molecules like carboxyfluorescein. The variant peptide with the lysine residue in the hydrophobic region also has the ability to perturb lipid bilayers of model membranes. 相似文献
12.
Pilar Nicolás 《Inorganica chimica acta》2005,358(5):1494-1500
Reaction of the disilylcyclopentadiene 1,1-[SiMe2(CH2CHCH2)]2C5H4 with NbCl5 gave the new allylsilyl-substituted monocyclopentadienyl niobium complex [Nb{η5-C5H4SiMe2(CH2CHCH2)}Cl4]. This compound was reacted with LiNHtBu or NH2tBu to give the imido derivative [Nb{η5-C5H4SiMe2(CH2CHCH2)}(NtBu)Cl2], which was further alkylated to the imido alkyl complexes [Nb{η5-C5H4SiMe2(CH2CHCH2)}(NtBu)R2] (R = Me, CH2Ph) and [Nb{η5-C5H4SiMe2(CH2CHCH2)}(NtBu)Cl (CH2Ph)]. Reaction of the imido complexes with the corresponding lithium cyclopentadienides gave the dicyclopentadienyl-imido complexes [M(η5-C5R5){η5-C5H4SiMe2(CH2CHCH2)}(NtBu)Cl] (M = Nb, Ta; R = H, Me). Metallocene dichlorides [M(η5-C5R5){η5-C5H4SiMe2(CH2CHCH2)}Cl2] (M = Nb, Ta; R = H, Me) were easily prepared by reduction with Na/Hg and simultaneous transmetallation of [Ta(η5-C5R5)Cl4] with Li[C5H4SiMe2(CH2CHCH2)] and of [Nb{η5-C5H4SiMe2(CH2CHCH2)}Cl4] with Li(C5R5). All of the new compounds have been characterized by elemental analysis, and IR and NMR spectroscopy. 相似文献
13.
Antonio Antiñolo Rafael Fernández-Galán Antonio Otero Ana M. Rodríguez 《Inorganica chimica acta》2010,363(13):3489-3497
New C-ansa-zirconocene complexes containing methoxythiophenolate and mercaptophenolate ligands have been synthesized and characterized. The reaction of (HSC6H4-n-OMe) (n = 2, 3 or 4) with [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}Me2] (1) led to the formation of monosubstituted complexes [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}Me(κ,S-SC6H4-n-OMe)] (n = 2 (2); n = 3 (3)) and the disubstituted complex [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}(κ,S-SC6H4-4-OMe)2] (4). The complexes [Zr{(R)HC(η5-C5Me4)(η5-C5H4)}(κ,O-OC6H4-4-SH)2] (R = t-Bu (6); R = CH2CHCH2 (7)) and [Zr(η5-C5H4)2(OC6H4-n-SH)2] (n = 3 (9); n = 4 (10)) have been synthesized using the corresponding dimethyl zirconocene and mercaptophenol. However, the reaction of [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}Cl2] (11) with 4-mercaptophenol in the presence of NEt3 led to the formation of the first example of a homoleptic six-coordinate mercaptophenolate complex of zirconium, namely [HNEt3]2[Zr(κ,O-OC6H4-4-SH)6] (12). Complex 12 can be obtained in higher yield by the reaction of ZrCl4 with six equivalents of 4-mercaptophenol and NEt3. The reaction of 12 with [Zr(η5-C5H4)2Cl2] gave the unexpected disubstituted complex [Zr(η5-C5H4)2(OC6H4-4-SH)2] (10). The molecular structures of 4 and 12 have been determined by single-crystal X-ray diffraction studies. 相似文献
14.
Complexes [Ag(NH2R)2]X, (X = NO3, R = -C6H4-CnH2n+1-p, -C6H4-O-CnH2n+1-p, -CH2-C6H4-O-CnH2n+1-p, n = 6, 8, 10, 12, 14; X = BF4, R = -CH2-C6H4-O-CnH2n+1-p, n = 6, 8, 10, 12, 14; X = OAc, R = -CH2-C6H4-O-C10H21-p; X = CF3SO3, R = -CH2-C6H4-O-C10H21-p) have been prepared. They all show SA mesophases corresponding to two kinds of structures, already present in the solid state. The alkylaniline and alkoxyaniline derivatives adopt a bilayered structure where the cation has an extended centrosymmetric conformation. The benzylamine derivatives contain U-shaped cations giving rise to a bilayered structure which allows microsegregation of the organic part of the molecule from the inorganic Ag?(anion) part. Some degree of interdigitation of the terminal chains is observed for all the complexes with aryl containing ligands. 相似文献
15.
The dinuclear arene ruthenium complexes [RuCl2{C6H5(CH2)3OCO-p-C6H4-OC8H17}]2 (1) and [RuCl2{p-C6H4(CH2COOCH2CH3)2}]2 (2) have been obtained by dehydrogenation of the corresponding cyclohexadiene derivative with ruthenium chloride hydrate. The single-crystal X-ray structure analysis of 2 shows the arene ligands to be involved in slipped-parallel π-π stacking interactions with neighbouring molecules, thus forming infinite chains along the b-axis. The dinuclear complexes 1 and 2 react with two equivalents of triphenylphosphine (PPh3) to give in excellent yield the corresponding mononuclear phosphine complexes [RuCl2{C6H5(CH2)3OCO-p-C6H4-OC8H17}(PPh3)] (3) and [RuCl2{p-C6H4(CH2COOCH2CH3)2}(PPh3)] (4), respectively. The single-crystal X-ray structure analysis of 4 reveals the formation of a dimer through two C-H?Cl interactions in the solid state. 相似文献
16.
Fuwu Ji Huaiyang Zhou Qunhui Yang 《Origins of life and evolution of the biosphere》2008,38(2):117-125
Conversion of CO2 to organic compounds in hydrothermal systems is important in understanding prebiotic chemical evolution leading to the origin
of life. However, organic compounds with carbon number of more than 3 have never been produced from dissolved CO2 in simulated hydrothermal experiments. In this paper, we report that not only CH4, C2H6 and C3H8, but also n-C4H10 and n-C5H12 could be produced from dissolved CO2 and H2 in the presence of cobalt-bearing magnetite at 300°C and 30 MPa. It is shown that unbranched alkanes in Anderson–Schulz–Flory
distribution were the dominant hydrocarbon products produced from dissolved CO2 catalyzed by cobalt-bearing magnetite under certain hydrothermal conditions. It is proposed that magnetite with other transition
metals may act potentially as effective mineral catalysts for abiotic formation of organic compounds from dissolved CO2 in hydrothermal systems. 相似文献
17.
《Biochimica et Biophysica Acta (BBA)/General Subjects》2005,1722(2):224-233
The biological properties of bisquaternary ammonium salts, which are derivatives of N,N-bisdimethyl-1,2-ethanediamine (bis-CnBEC), of general formula /CnH2n+1OOCCH2(CH3)2N+CH2CH2N+(CH3)2CH2COOCnH2n+1/2Cl−, were investigated (n=10, 12, 14). The interaction with model membrane was studied by differential scanning calorimetry experiments, and the apparent adiabatic molar compressibility of their solution as a function of concentration was obtained by sound velocity measurements. Their biological activities were assayed by Electrophoresis Mobility Shift, MTT proliferation, and transient transfection. All the investigated compounds interact with the DNA and are able to transfect DNA, when they are coformulated with DOPE, with an efficiency significantly greater than that of a standard commercial transfection reagent. Bis-C14BEC is the only molecule able to deliver DNA inside the cells without a helper lipid, as shown by EGFP expression, albeit with a low efficiency in comparison with a standard commercial transfection reagent. This may be due to a slightly different interaction of bis-C14BEC from bis-C10BEC and bis-C12BEC with phospholipid bilayers. Bis-C10BEC and bis-C12BEC show a slight fluidising effect, while bis-C14BEC increases stability of both the gel and the rippled gel phases. 相似文献
18.
We have used isothermal titration calorimetry (ITC) to study the thermodynamics of Triton X-100 (TX-100), deoxycholate and decyl octaethylene glycol (C10EO8) penetration into bilayers composed of native (ESM) and hydrogenated egg yolk sphingomyelin (DHSM). Light scattering measurements were used to study the point of saturation (Re,sat) and the onset of solubilization of membranes by the detergents. We found that DHSM bilayers at 25 °C were much more resistant to detergent partitioning (lower K) and gave higher reaction enthalpies (ΔH) for all three detergents compared to the ESM bilayer system. Because DHSM lacks double bonds (Δ4trans and some cis bonds as well), attractive acyl chain interactions are favored in membranes of this lipid class. The high stability and cohesion of DHSM in membranes could be a crucial functional property of this lipid as it is enriched in eye lens membranes. 相似文献
19.
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
20.
Hisashi Nishiwaki Maya Ouchi Junko Matsugi Koichi Akiyama Takuya Sugahara Taro Kishida Satoshi Yamauchi 《Bioorganic & medicinal chemistry letters》2012,22(21):6740-6744
Using 21 newly synthesized 7,7′-dioxo-9,9′-epoxylignane derivatives having a modified 7-phenyl group, we examined the relationship between their structure and antifungal activity against plant pathogens such as Bipolaris oryzae to determine the effects of various substituents on the antifungal activity. Compared with the lead compound having a 4-OH-3-CH3O-phenyl moiety, several analogs showed higher antifungal activity against B. oryzae, including the compound having an unsubstituted phenyl group and those having either of the following phenyl substituents: 2-OH, 4-CH3O, 4-C2H5O, 4-n-C3H7O, 4-n-C4H9O, 4-CF3O, 4-C2H5, or 4-Cl. On the other hand, the activity of compounds having a branched substituent, such as 4-i-C3H7O or 4-i-C3H7, on the 7-phenyl group or a multi-substituted phenyl group was equipotent or inferior to that of the lead compound. These results as well as correlations between the antifungal activity of the test compounds and the physicochemical parameters of the varied substituents suggest that the position of substitution on the 7-phenyl group and the incorporation of substituents with optimal physicochemical properties are important for exerting the antifungal activity. 相似文献