共查询到20条相似文献,搜索用时 31 毫秒
1.
D. E. Stepanov L. V. Grishchuk R. Yu. Ivanova Yu. E. Ivanov A. A. Yavolovskii G. L. Kamalov 《Russian Journal of General Chemistry》2013,83(3):526-529
The synthesis of 2-(2-amino-4-arylthiazol-5-yl)pyrimidin-4(3H)-ones from the available 2-(2-oxo-2-arylethylidene)-2,3-dihydropyrimidin-4(1H)-ones was developed. 相似文献
2.
Munetaka Akita Masako Terada Masako Tanaka Yoshihiko Morooka 《Journal of organometallic chemistry》1996,510(1-2):255-261
The structures of the versatile starting compounds for organoiron complexes, the cationic aqua complex [(η5-C5Me4Et)Fe(CO)2(OH2)]BF4 (1b) and the halide complexes (η5-C5Me5)Fe(CO)2-I (2a), (η5-C5Me4Et)Fe(CO)2-I (2b) and (η5-C5Me4Et)Fe(CO)2-Cl (3b), are characterized by X-ray crystallography. Complex 1b [Fe---O: 2.022(8) Å and 2.043(9) Å, two independent molecules] is the first structurally characterized example of organoiron aqua complexes. Details of the synthetic procedures for the above complexes and the labile cationic THF complexes [η5-C5R5)Fe(CO)2(THF)]BF4 (4) are disclosed, and the dissociation equilibrium of 4 is confirmed by means of variable temperature 1H-NMR as well as saturation transfer experiment. 相似文献
3.
The complexes [WI2(CO)L2(η2-RC2R)] (L = PEt3 or PMe2Ph; R = Me or Ph) react with an equimolar quantity of Ag[BF4] in acetonitrile at room temperature to give good yields of the new purple cationic alkyne complexes [WI(CO)(NCMe)L2(η2-RC2R)][BF4]. 31P NMR spectroscopy indicates that the phosphines are trans to each other in these compounds. 13C NMR spectroscopy suggests that the alkyne ligands are donating four electrons to the tungsten in these complexes. 相似文献
4.
Polycatenar saturated macrocycles 1,10-bis[3,4,5-tris(4-dodecyloxy)benzoy1]-1,10-diaza-4,7,13,16-tetrathiacyclo-octadecane (3b) and 1,10-bis[3,4-bis(4-dodecyloxy)benzoy1] -1,10-diaza-4,7,13,16-tetrathiacyclo-octadecane (3d) reacted with [Pd(MeCN)4][BF4]2 led to the cationic complexes [4b][BF4]2 and [4d][BF4]2, respectively. Complexes [4b][BF4]2 and [4d][BF4]2 showed smectic mesomorphism on heating as confirmed by small angle X-ray diffraction. A concurrent, irreversible structural change of the complex cations was observed and a tentative explanation is suggested. 相似文献
5.
Three novel lanthanide complexes [Ln(3,4-DEOBA)3phen]2[Ln=Eu(1), Tb(2), Dy(3); 3,4-DEOBA=3,4- diethoxybenzoate; phen=1,10-phenanthroline] were synthesized and characterized by elemental analysis, molar conductance, X-ray diffraction and infrared spectrometry. The luminescence spectra of complexes 1 and 2 show the characteristic emission of Eu3+ ion(5D0→7F0-3) and Tb3+ ion(5D4→7F6-3). The thermal decomposition mechanism of the title complexes and the analysis of the evolved gases were investigated by thermogravimetry/differential scanning calorimetry-Fourier transform infrared(TG/DSC-FTIR) technology. The results indicate the complexes are thermally stable. In the thermal decomposition of the complexes, phen molecules lost firstly, and then 3,4-DEOBA ligand decomposed into H2O, CO2 and other gaseous molecules. Besides, several gaseous organic fragments were also detected. The heat capacities of complexes 1―3 were measured by DSC in a temperature range of 263.15―340.15 K. Based on the fitted polynomial and thermodynamic equations, the smoothed heat capacities and thermodynamic functions of the three complexes were calculated. The study on biological activity showed that the complexes exhibited good antibacterial activity against Candida albicans, Staphylococcus aureus and Escherichia coli. 相似文献
6.
Matthias Haufe Randolf D. Khn Roman Weimann Guido Seifert Dieter Zeigan 《Journal of organometallic chemistry》1996,520(1-2):121-129
Diethylzinc reacts with hydroperchlorates of N-alkylated 1,3,5-triazacyclohexanes (R3TAC; R = methyl (Me), benzyl (Bz), isopropyl (iPr)) and with the hydrotetrafluoroborate of 1,3,5-tris-(para-fluorobenzyl)-1,3,5-triazacyclohexane (FBz3TAC) to give the corresponding cationic zinc ethyl complexes [(R3TAC)Zn(Et)][X] (X = ClO4−, BF4−). Similar complexes were obtained from diethylzinc treated with [HNMe2Ph][BF4] or [HNMe2Ph][B(C6F5)4](Et2O) in the presence of R3TAC (R = Bz, FBz, s-1-phenylethyl (s-PhMeCH)). A product of decomposition of [(Bz3TAC)Zn(Et)][ClO4] was analyzed by X-ray diffraction. The structures of [({s-PhMeCH}3TAC)Zn(Et)][BF4] an [(FBz3TAC)Zn(Et)][BF4] were estimated using nuclear Overhauser enhancement spectroscopy. Protonolysis of diethylzinc with [HNMe2Ph][BF4] in the presence of 13-benzyl-1,5,9-triazatricyclo[7.3.1.05,13]-tridecane (BzTATC) yielded the complex [(BzTATC)Zn(Et)][BF4]. 相似文献
7.
Three novel uranyl complexes with organic phosphine oxide ligands and bridging fluorides have been synthesised and structurally characterised. In [ UO2(μ-F)(TPPO)3 2][BF4]2 · nC6H14, 1, and [ UO2(-μF)(TBPO)3 2][BF4]2 2, (where TPPO and TBPO are triphenylphosphine oxide and tri-n-butylphosphine oxide, respectively) two UO2 2+ moieties are bridged by two fluorides with three additional terminal PO donor ligands coordinated to each uranium centre. The dicationic complexes are both charge balanced by two uncoordinated tetrafluoroborate anions. In the related structure, [UO2(μ-F)(F)(DPPMO2)]2 · 2MeOH (3), terminal fluoride is also coordinated to both uranyl centres (where DPPMO2 = bis(diphenylphosphine oxide)methane). All three complexes were prepared during attempted syntheses of complexes with tetrafluoroborate directly coordinated to uranium. It is clear from these results that the fluorophilicity of UO2 2+ causes the abstraction of fluoride from [BF4]−, with the weakly coordinating anion only present as a counter cation in 1 and 2, and absent completely in 3. 相似文献
8.
Reaction of potassium 3{5}-(3′,4′-dimethoxyphenyl)pyrazolide with 2-bromopyridine in diglyme at 130°C for 3 days followed by an aqueous quench, affords 1-{pyrid-2-yl}-3-{3′,4′-dimethoxyphenyl}pyrazole (L2) in 69% yield after recrystallization from hot hexanes. Complexation of [Cu(NCMe)4]BF4 by 2 molar equivalents of 1-{pyrid-2-yl}-3-{2′,5′-dimethoxyphenyl}pyrazole (L1) or L2 in MeCN at room temperature, followed by concentration and crystallisation with Et2O, gives [Cu(L)2]BF4 L = L1, L2) in good yields. Treatment of AgBF4 with L1 or L2 in MeNO2 similarly gives [Ag(L)2]BF4 L = L1, L2); reaction of AfBF4 with L2 in MeCN gives a product of stoichiometry [Ag(L2)(NCMe)]BF4. The 1H NMR spectra of the [M(L)2]BF4 complexes show peaks arising from a single coordinated environment. The single crystal X-ray structure of [Cu(L1)2]BF4 shows a tetrahedral complex cation with Cu---N = 2.011(8), 2.036(8), 2.039(8), 2.110(8) Å. The CuI centre is close to tetrahedral, the dihedral angle between the least-squares planes formed by the Cu atom and the N donor atoms of the two ligands being 88.3(3)°. Complexation of hydrated Cu(BF4)2 by L2 in MeCN at room temperature yields [Cu(L2)2](BF4)2. The cyclic voltammograms of the three AgI complexes in MeCN/0.1 M Bu4n NPF6 are suggestive of extensive ligand dissociation in this solvent. 相似文献
9.
The stereochemistry and regiochemistry of nucleophilic addition to olefinic, allylic, or diene moieties can be controlled in reactions of molybdenum complexes. The synthesis of a wide range of -allylic cyclohexanones is feasible using (η5-cyclopentadienyl)Mo(CO)(NO)(allyl) cations. The stereoselective preparation of (RS,SR)-2-(1-methyl-2-butenyl)cyclohexanone from the reaction of 1-pyrrolidino-1-cyclohexene with [CpMo(CO)(NO)(η3-1,3-dimethylallyl)]BF4 illustrates the methodology. 相似文献
10.
Reaction of optically active ketone complexes (+)-(R)-[(η5-C5H5)Re(NO)-(PPh3)(η1-O=C(R)(CH3)]+ BF4− (R = CH2CH3, CH(CH3)2m C(CH3)3, C6H5) with K(s-C4H9)3BH gives alkoxide complexes (+)-(RS)-(η5-C5H5)Re(NO)(PPh3)-(OCH(R)CH3) (73–90%) in 80–98% de. The alkoxide ligand is then converted to Mosher esters (93–99%) of 79–98% de. 相似文献
11.
The oxidation of Cp2MCl2 (M= Mo, W) with perfluortriazinium tetrafluoroborate, [(FCN)3F]+[BF4]−, in the presence of a flouride ion acceptor (BF3 or PF5) in SO2 solution yielded the cationic metallocene complexes [Cp2MCl 2]2+[BF4]− or [Cp2MCl2] 2+[BF4]−[PF6]− (M = Mo, W), respectively. In these reactions, for the first time the perfluortriazinium cation has proved to be easy to handle and a useful oxidizer in organometallic chemistry. The oxidizer strength of three fluorotriazinium cations, [(XCN)3F]+ (X = F, Cl, H), has been computed ab initio (HF/6 − 31 + G) and calibrated on literature data which were obtained by local density functional calculations. It was anchored to its F+ zero point by an experimental value for KrF+. ab]Die Oxidation von Cp2MCl2 mit (M = MO, W) Perfluortriaziniumtetrafluoroborat, [(FCN)3F]+[BF4]−, in Anwesenheit eines Fluoridionenakzeptors (BF3 oder PF5) führte in SO2-Lösung zur Bildung der kationischen Metallocen-Komplexe [Cp2MCl2+]2+[BF4]2− bzw. [Cp2MCl2]2+[BF4]− [PF6]− (M = Mo, W). In diesen Reaktionen konnte erstmals gezeigt werden, daß Perfluortriazinium-Kationen einfach zu handhabende und nützliche Oxidationsmittel im Bereich der metallorganischen Synthese darstellen. Das (Mdationsvermögen von drei Fluorotriazinium-Kationen, [(XCN)3F]+(X = F, Cl, H), wurde ab initio berechnet (HF/6 − 31 + G) und mit Hilfe von Literaturdaten, die mittels local density functional-Berechnungen erhalten und am experimentellen Wert von KrF + bezüglich des F+ Nullpunktes verankert wurden, kalibriert. 相似文献
12.
Christopher S. Griffith George A. Koutsantonis Brian W. Skelton Allan H. White 《Journal of organometallic chemistry》2003,670(1-2):198-204
The acid–base chemistry of some ruthenium ethyne-1,2-diyl complexes, [{Ru(CO)2(η-C5H4R)}2(μ2-CC)] (R=H, Me) has been investigated. Initial protonation of [{Ru(CO)2{η-C5H4R}}2(μ2-CC)] gave the unexpected complex cation, crystallised as the BF4 salt, [{Ru(CO)2(η-C5H4R}}3(μ3-CC)][BF4] (R=Me structurally characterised). This synthesis proved to be unreliable but subsequent, careful protonation experiments gave excellent yields of the protonated ethyne-1,2-diyl complexes, [{Ru(CO)2{η-C5H4R)}2(μ2-η1:η2-CCH)](BF4) (R=Me structurally characterised) which could be deprotonated in high yield to return the starting ethyne-1,2-diyl complexes. 相似文献
13.
A. A. Yavolovskii L. V. Grishchuk E. I. Bevzyuk Yu. E. Ivanov D. E. Stepanov S. M. Pluzhnik-Gladyr G. L. Kamalov 《Russian Journal of General Chemistry》2014,84(5):869-874
2-(2-Oxo-2-arylethylidene)-2,3-dihydropyrimidine-4(1H)-ones react with aromatic and heteroaromatic aldehydes to form the unsaturated ketones, whereas in the case of 3- and 4-benzaldehydes the corresponding trans-2-styrylpyrimidine-4(3H)-ones were obtained. A possible mechanism of hydrolytic cleavage of the product of condensation of 2-(2-oxo-2-phenylethylidene)-2,3-dihydropyrimidine-4(1H)-one with paraformaldehyde under acid catalysis and mechanochemical activation has been discussed. 相似文献
14.
二苯并噻吩及其氧化物与离子液体相互作用的理论研究 《燃料化学学报》2012,40(12):1444-1453
采用密度泛函理论方法比较了DBT/DBTO2和[BMIM]+[PF6]-/[BMIM]+[BF4]-的相互作用。对最稳定的[BMIM]+[PF6]-、[BMIM]+[PF6]--DBT、[BMIM]+[PF6]--DBTO2、[BMIM]+[BF4]-、[BMIM]+[BF4]--DBT、[BMIM]+[BF4]--DBTO2进行了NBO和AIM分析。结果表明,DBT和[BMIM]+[PF6]-/[BMIM]+[BF4]-中的咪唑环彼此相互平行,NBO和AIM分析表明它们之间发生了π-π相互作用。H1'和H9'形成的F…H氢键有利于π-π堆积作用的形成。DBTO2倾向于趋近C2-H2和甲基基团形成O…H相互作用;DBTO2优先吸附在[BMIM]+[PF6]-/[BMIM]+[BF4]-。在模拟油中,[BMIM]+[PF6]-和[BMIM]+[BF4]-离子液体对DBTO2的萃取能力大于DBT,其原因是可能是DBTO2具有较大的极性和O…H与F…H的氢键作用。 相似文献
15.
Kenzo Ohkita Hideo Kurosawa Toshikazu Hirao Isao Ikeda 《Journal of organometallic chemistry》1994,470(1-2):179-182
Some (η5-cyclopentadienyl)(1,2-bis(diarylphosphino)ethane)(diorganosulfide)ruthenium complexes, [Ru(η5-C5H5)(Ar2PCH2CH2-PAr2)(R1R 2S)]BF4 (Ar = Ph, p-Tol; R1, R2 = Ph, Et) were prepared. Variable temperature NMR spectra of these complexes showed the existence of two fluxional processes; inversion at the sulfur atom and δ-λ interconversion of the chelate ring. The former process was slower, and its barriers in these complexes were calculated as ca. 7 kcal mol−1. The spectral features of ethyl phenyl sulfide complexes suggested that substantiation of the new chiral center at sulfur induces a significant conformational rigidity at the chelate ring. 相似文献
16.
The reaction of K[ReH6(PPh3)2] with [RhCl(CO)L2] [L= PPh3, 1,2,5-triphenylphosphole (TPP), or P(OMe)3] leads to the new electronically unsaturated heterobimetallic polyhydride complexes [(CO)(PPh3)2HRe(μ-H)3RhL2] in moderate-to-good yields. The structures of these complexes have been established on the basis of spectroscopic data, especially 1H and 31P NMR. The bridging hydride ligands are fluxional but there is either a slow or nonexistent exchange between terminal and bridging hydrides. For L = PPh3 or TPP, protonation with tetrafluoroboric acid affords quantitatively the cationic complexes [(CO)(PPh3)2HRe(μ-H)3RhHL2]+, isolated as the BF4− or the BPh4− salts. 相似文献
17.
The reaction of [(CO)PPh3)2Re(μ-H)2(μ-NCHPh)Ru(PPh3)2(PhCN)] (2) with HBF4-Me2O generates [(CO)PPh3)2Re(μ- H)2(μ,η1,η2HNCHPh)Ru(PPh3)2(PhCN)][BF4] (3). Monitoring the reaction by NMR spectroscopy shows the intermediate formation of [(CO)(PPh3)2 HRe(μ-H)2(μ-NCHPh)Ru(PPh3)2(PhCN)][BF4] (4). Attempted reduction of the imine ligand by a nucleophile (H− or CN−) failed, regenerating 2. Under dihydrogen at 50 atm, 3 is slowly transformed into [(CO)(PPh3)2HRe(μ-H)3Ru(PPh3)2(PhCN)][BF4] (5) with liberation of benzyl amine. 相似文献
18.
J.S. Casas M.V. Castao M.S. García-Tasende A. Snchez J. Sordo A. Touceda 《Polyhedron》2005,24(18):9871-3065
The reaction of zinc(II) acetate with thiosemicarbazones derived from β-keto esters (methyl propionylacetate thiosemicarbazone, ethyl benzoylacetate thiosemicarbazone, ethyl 2-ethylacetoacetate thiosemicarbazone and methyl acetoacetate 1N-ethylthiosemicarbazone) induces the cyclization of the thiosemicarbazone to afford [ZnL2] and (in one case) [ZnL2(MeOH)] complexes, where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazolone-1-carbothioamide. The four complexes were studied by X-ray diffraction, which showed that the pyrazolonate ligand binds with the metal through the S and N(3) atoms. The influence of cyclization and metallation on the 1H and 13C NMR spectra of the starting thiosemicarbazones is also discussed. 相似文献
19.
K. Laihia A. Valkonen E. Kolehmainen A. Antonov D. Zhukov I. Fedosov V. Nikiforov 《Journal of Molecular Structure》2006,800(1-3):100-105
Three spiro[pyrrolidine-2,3′-oxindoles], 1,1′,2,2′,5′,6′,7′,7′a-octahydro-2-oxo-1′-phenyl-spiro[3H-indole-3,3′-[3H]-pyrrolizine]-2′-carboxylic acid methyl ester (1), 1,1′,2,2′,5′,6′,7′,7′a-octahydro-2-oxo-1′-nitro-2′-phenyl-spiro[3H-indole-3, 3′-[3H]-pyrrolizine] (2) and 1,1′,2,2′,5′,6′,7′,7′a-octahydro-2-oxo-1′-nitro-2′-(4″-chlorophenyl)-spiro[3H-indole-3,3′-[3H]-pyrrolizine] (3) have been synthesized and their 1H, 13C and 15N spectra assigned. The chemical shift assignments are based on Pulsed Field Gradient (PFG) Double Quantum Filter (DQF) 1H, 1H correlation spectroscopy (COSY), PFG 1H, 13C Heteronuclear Multiple Quantum Coherence (HMQC) and PFG 1H,X (X = 13C and 15N) Heteronuclear Multiple Bond Correlation (HMBC) experiments. The single crystal X-ray structures of 1–3 have been determined. Compounds 1 and 2 crystallized in monoclinic space group C2/c and compound 3 in monoclinic space group P21/c, respectively. Also the ESI-TOF MS data of 1–3 are given. 相似文献
20.
Helmut Fischer David Reindl Carsten Troll 《Journal of organometallic chemistry》1994,480(1-2):221-225
The successive reaction of chromium and tungsten hexacarbonyl, (CO)6M (M = Cr, W), with [N=C(Ph)R]− and [Et3O]BF4 yields the alkylideneamino(ethoxy)carbene complexes (CO)5M[C(OEt)N=C(Ph)R] (M = Cr (1), W (2); R = NMe2 (a), tBu (b)). Ethoxide abstraction from 1 and 2 affords 2-azoniaallenylidene complexes, {(CO)5M[CNC(Ph)R]}+BF4− (3/4). The complexes 3 and 4 are best described as resonance hybrids of several limiting structures. On the basis of the spectroscopic data of the complexes 3a and 4a the limiting structure of an iminium-substituted isocyanide complex dominates. 相似文献