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1.
The reaction of 9,10-phenanthrenequinone (PQ) with [M(II)(H)(CO)(X)(PPh(3))(3)] in boiling toluene leads to the homolytic cleavage of the M(II)-H bond, affording the paramagnetic trans-[M(PQ)(PPh(3))(2)(CO)X] (M = Ru, X = Cl, 1; M = Os, X = Br, 3) and cis-[M(PQ)(PPh(3))(2)(CO)X] (M = Ru, X = Cl, 2; M = Os, X = Br, 4) complexes. Single-crystal X-ray structure determinations of 1, 2·toluene, and 4·CH(2)Cl(2), EPR spectra, and density functional theory (DFT) calculations have substantiated that 1-4 are 9,10-phenanthrenesemiquinone radical (PQ(?-)) complexes of ruthenium(II) and osmium(II) and are defined as trans-[Ru(II)(PQ(?-))(PPh(3))(2)(CO)Cl] (1), cis-[Ru(II)(PQ(?-))(PPh(3))(2)(CO)Cl] (2), trans-[Os(II)(PQ(?-))(PPh(3))(2)(CO) Br] (3), and cis-[Os(II)(PQ(?-))(PPh(3))(2)(CO)Br] (4). Two comparatively longer C-O [average lengths: 1, 1.291(3) ?; 2·toluene, 1.281(5) ?; 4·CH(2)Cl(2), 1.300(8) ?] and shorter C-C lengths [1, 1.418(5) ?; 2·toluene, 1.439(6) ?; 4·CH(2)Cl(2), 1.434(9) ?] of the OO chelates are consistent with the presence of a reduced PQ(?-) ligand in 1-4. A minor contribution of the alternate resonance form, trans- or cis-[M(I)(PQ)(PPh(3))(2)(CO)X], of 1-4 has been predicted by the anisotropic X- and Q-band electron paramagnetic resonance spectra of the frozen glasses of the complexes at 25 K and unrestricted DFT calculations on 1, trans-[Ru(PQ)(PMe(3))(2)(CO)Cl] (5), cis-[Ru(PQ)(PMe(3))(2)(CO)Cl] (6), and cis-[Os(PQ)(PMe(3))(2)(CO)Br] (7). However, no thermodynamic equilibria between [M(II)(PQ(?-))(PPh(3))(2)(CO)X] and [M(I)(PQ)(PPh(3))(2)(CO)X] tautomers have been detected. 1-4 undergo one-electron oxidation at -0.06, -0.05, 0.03, and -0.03 V versus a ferrocenium/ferrocene, Fc(+)/Fc, couple because of the formation of PQ complexes as trans-[Ru(II)(PQ)(PPh(3))(2)(CO)Cl](+) (1(+)), cis-[Ru(II)(PQ)(PPh(3))(2)(CO)Cl](+) (2(+)), trans-[Os(II)(PQ)(PPh(3))(2)(CO)Br](+) (3(+)), and cis-[Os(II)(PQ)(PPh(3))(2)(CO)Br](+) (4(+)). The trans isomers 1 and 3 also undergo one-electron reduction at -1.11 and -0.96 V, forming PQ(2-) complexes trans-[Ru(II)(PQ(2-))(PPh(3))(2)(CO)Cl](-) (1(-)) and trans-[Os(II)(PQ(2-))(PPh(3))(2)(CO)Br](-) (3(-)). Oxidation of 1 by I(2) affords diamagnetic 1(+)I(3)(-) in low yields. Bond parameters of 1(+)I(3)(-) [C-O, 1.256(3) and 1.258(3) ?; C-C, 1.482(3) ?] are consistent with ligand oxidation, yielding a coordinated PQ ligand. Origins of UV-vis/near-IR absorption features of 1-4 and the electrogenerated species have been investigated by spectroelectrochemical measurements and time-dependent DFT calculations on 5, 6, 5(+), and 5(-). 相似文献
2.
A catalytic photometric method with a flow-injection system is described for the determination of 9,10-phenanthrenequinone. It is based on the catalytic effect of 9,10-phenanthrenequinone on the redox reaction of 1,2-dinitrobenzene with formaldehyde under alkaline conditions. 9,10-Phenanthrenequinone at the 5.0 x 10(-8)-5.0 x 10(-6)M level can be determined at a rate of 20 samples/hr. The detection limit is 1.0 x 10(-8)M (40 pg in a 10-microl injection). 相似文献
3.
4.
A. M. Andrievskii R. V. Linko M. K. Grachev 《Russian Journal of Organic Chemistry》2013,49(7):1025-1030
The reaction of 2,4,7-trinitro-9,10-phenanthrenequinone with CuCl in aqueous dimethylformamide or dimethyl sulfoxide at room temperature, followed by acidification, gave a stable red complex of 2,4,7-trinitro-9,10-dihydroxyphenanthrene with a solvent molecule. On heating in a polar aprotic solvent in the presence of CuCl or other metal salt, 2,4,7-trinitro-9,10-phenanthrenequinone underwent benzilic acid rearrangement with formation of 2,4,7-trinitrofluorenone. The nitration of 9,10-sulfuryldioxyphenanthrene and subsequent decomposition of cyclic sulfates afforded previously unknown 1,3,6-trinitro- and 1,8-dinitro-9,10-phenanthrenequinones. 相似文献
5.
The oxygen dependent cleavage of 9, 10-phenanthrenequinone by CuX (X=Cl, Br) with py, dipy, and phen ligands to well define copper(II) diphenato complexes and evidence for the intermediate Cu–O2 complexes containing CuII and CuI are reported.
9,10- CuX (X=Cl, Br) py, dipy phen (II), , , Cu–O2, CuII CuI.相似文献
6.
Rabab Boyaala Rafika El Ati Mohamed Khoutoul Mohamed El Kodadi Rachid Touzani Belkheir Hammouti 《Journal of the Iranian Chemical Society》2018,15(1):85-92
In the present work, catecholase activity is presented. The complexes were prepared by condensation of the organic ligand pyrazolyl L 1 –L 4 and copper(II) ion in situ. The pyrazolyl compounds L 1 –L 4 used in this study are: L 1 is (3,5-dimethyl-pyrazol-1-ylmethyl)-(4-methyl-pyridin-2-yl)-pyrazol-1-ylmethyl-amine; L 2 is 1-{4-[(3,5-dimethyl-pyrazol-1-ylmethyl)-pyrazol-1-ylmethyl-amino]-phenyl}-ethanone; L 3 is 1-{4-[(3,5-dimethyl-pyrazol-1-ylmethyl)-[1,2,4]triazol-1-ylmethyl-amino]-phenyl}-ethanone, and L 4 is 2-[(3,5-dimethyl-pyrazol-1-ylmethyl)-[1,2,4]triazol-1-ylmethyl-amino]-6-methyl-pyrimidin-4-ol, and copper ions salts Cu(II) are (Cu(CH3COO)2, CuCl2, Cu(NO3)2 and CuSO4). In order to determine factors influencing the catecholase activity of these complexes, the effect of ligand nature, ligand concentration, nature of solvent and nature of counter anion has been studied. The best activity of catechol oxidation is given by the combination formed by one equivalent of ligand L 2 and one equivalent of Cu(CH3COO)2 in methanol solvent which is equal to 9.09 µmol L?1 min?1. The Michaelis–Menten model is applied for the best combination, to obtain the kinetic parameters, and we proposed the mechanism for oxidation reaction of catecholase. 相似文献
7.
《Journal of Coordination Chemistry》2012,65(19):3537-3550
A series of palladium complexes, [PdCl(L1–4)] (1–4) (L1 = 9,10-phenanthrenequinone thiosemicarbazone, L2 = 9,10-phenanthrenequinone methylthiosemicarbazone, L3 = 9,10-phenanthrenequinone phenylthiosemicarbazone, and L4 = 9,10-phenanthrenequinone semicarbazone), have been synthesized and characterized by elemental analyses, UV–vis, FT-IR, 1H and 13C NMR, and ESI-Mass spectroscopic methods. The catalytic efficiency of the synthesized complexes was examined against N-arylation of imidazole. The system works well with the electron-rich, -neutral, and -deficient aryl halides to afford the products in good to excellent yields. Sterically congested aryl halides and heteroaryl halides have also been used as substrates to provide N-arylated heterocycles. In addition, this methodology can be applicable to other substrates with N-containing heterocycles. 相似文献
8.
Roman Linko Michael Ryabov Pavel Strashnov Pavel Dorovatovskii Victor Khrustalev Victor Davydov 《Molecules (Basel, Switzerland)》2021,26(21)
Understanding the interactions of organic donor and acceptor molecules in binary associates is crucial for design and control of their functions. Herein, we carried out a theoretical study on the properties of charge transfer complexes of 1,3,6-trinitro-9,10-phenanthrenequinone (PQ) with 23 aromatic π-electron donors. Density functional theory (DFT) was employed to obtain geometries, frontier orbital energy levels and amounts of charge transfer in the ground and first excited states. For the most effective donors, namely, dibenzotetrathiafulvalene, pentacene, tetrathiafulvalene, 5,10-dimethylphenazine, and tetramethyl-p-phenylenediamine, the amount of charge transfer in the ground state was shown to be 0.134−0.240 e−. Further, a novel charge transfer complex of PQ with anthracene was isolated in crystalline form and its molecular and crystal structure elucidated by single-crystal synchrotron X-ray diffraction. 相似文献
9.
Anangamohan Panja Sanchita Goswami Nizamuddin Shaikh Partha Roy Mario Manassero Ray J. Butcher Pradyot Banerjee 《Polyhedron》2005,24(18):2921-2932
The reaction of copper chloride dihydrate and ferric chloride hexahydrate with a tripodal N4 ligand (ntb) under mild conditions affords two novel complexes [Cu(ntb)Cl]2[CuCl4] · 2H2O (1) and [Fe(ntb)Cl2]Cl · 3H2O (2). The reaction of ferric chloride with another N4 ligand, bispicpn, forms an octahedral mononuclear complex, [Fe(bispicpn)Cl2]Cl (3). Single-crystal X-ray structural studies of 1, 2 and 3 reveal the formation of hydrogen-bond sustained 3D, 2D and 1D networks, respectively, involving (N–HO) and (N–HCl) interactions. The packing arrangement in 2 further reveals the existence of hexagonal channels with helical propagation along the diagonal of the crystallographic b- and c-axes. The reactions of these complexes with 3,5-di-tert-butylcatechol have been studied in dimethylformamide. NMR techniques have been used to identify the reaction products. 相似文献
10.
R. V. Linko V. A. Soldatkina B. E. Zaitsev M. A. Ryabov V. I. Sokol 《Russian Chemical Bulletin》1999,48(6):1095-1099
Phenanthrenequinone monoxime and its mono-, di-, and trinitro derivatives were synthesized. The acidity constants and their
variation with the number and position of nitro groups were determined. The electronic and IR spectra of the nitro compounds
were studied. The bands in the electronic spectra were assigned based on quantum-chemical calculations in the Pariser—Parr—Pople
approximation. Correlations between the pK
a values and some calculated characteristics of the compounds under study were found.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1106–1110, June, 1999. 相似文献
11.
《Journal of Coordination Chemistry》2012,65(8):1459-1474
New copper complexes of DL-methioninoylsulfadiazine (MTS) and L-cystinoylsulfadiazine (CYS) were prepared and characterized using elemental analysis, IR, electronic spectroscopy, EPR spectroscopy, and thermal analysis. The mode of binding indicates that copper binds to MTS through carbonyl oxygen with the amino group nitrogen while for CuII–CYS the copper binds through carbonyl oxygen and SH with removal of its proton. The proposed structures were supported by conformational analysis which showed predominance of the trans form of copper(II)-L-cystinoylsulfadiazine. The two complexes enhanced oxidation of phenol and catechol in the presence of H2O2 under mild conditions. The catalyst shows proficiency toward oxidation of phenol and catechol compared to the auto-catalytic oxidation. CuII–MTS exhibited higher catalytic activity than CuII–CYS. The phenol and catechol oxidation is inhibited by Kojic acid. 相似文献
12.
M. Huang M. M. Kireenko K. V. Zaitsev Yu. F. Oprunenko A. V. Churakov S. S. Karlov G. S. Zaitseva 《Chemistry of Heterocyclic Compounds》2012,47(12):1584-1589
A study was carried out on the behavior of monomeric germylenes derived from pyridine-containing diols in reactions with diphenylphosphoryl
azide and 9,10-phenanthrenequinone. It was found that the germanium atom increases its oxidation state to 4+ in these reactions.
The structure of the product of the reaction with 9,10-phenanthrenequinone was confirmed by X-ray structural analysis, which
showed a transannular germanium-nitrogen interaction in this product. 相似文献
13.
Erhan Zor Yasemin Oztekin Lina Mikoliunaite Jaroslav Voronovic Almira Ramanaviciene Zilvinas Anusevicius Haluk Bingol Arunas Ramanavicius 《Journal of Solid State Electrochemistry》2014,18(6):1529-1536
In this study, two ortho-quinoidal compounds, 1,10-phenanthroline-5,6-dione (PD) and 9,10-phenanthrenequinone (PQ), were examined as electron transfer mediators suitable for amperometric glucose biosensors. The dependences of the electrochemical responses of PD- and PQ-based amperometric glucose biosensors on varied concentrations of glucose were investigated under aerobic and anaerobic conditions. The PD-modified graphite rod (GR) electrode revealed a current response seven times higher than that of the PQ-modified GR electrode. The reactivity indices of ortho-quinoidals assessed by means of B3LYP functional method applying 6-311G(D) basis set showed that the electron-accepting potency for PD was markedly higher as compared with that of PQ. Compared to PQ, considerably higher reactivity of PD has been defined in the reactions with NADP+-ferredoxin reductase (FNR, EC 1.18.1.2) as a model single-electron transfer FAD-dependent enzyme, which provided an additional evidence for PD as a more efficient mediator compared to PQ. This study illustrates that PD can be applied as a redox mediator for glucose oxidase and it could be more suitable for a reagent-less biosensor design than PQ. 相似文献
14.
A reduction current is obtained when an aqueous solution of copper and catechol is subjected to differential-pulse cathodic stripping voltammetry (d.p.c.s.v.) because of the reduction of copper(II)—catechol complex ions which adsorb onto the hanging mercury drop electrode (HMDE). The most likely form of the adsorbed complex ions is CuL2?2 (L being catechol). A.c. polarographic measurements showed that these complex ions adsorb more strongly onto the drop than free catechol ions. Monolayer adsorption density is obtained at 2.1 × 10?10 molecules/cm2, equivalent to a surface area of 78 A2 complex ion, which agrees well with the molecular surface area calculated from the bond lengths. Analytically useful currents are obtained at very low metal concentrations, such as in uncontaminated sea water. The possible interference by other trace metals, major cations, and organic complexing ligands is investigated. Competition for copper ions by natural organic complexing ligands is evident at low concentrations of catechol. Analysis of the dissolved copper concentration in sea water by d.p.c.s.v. at the HMDE (at neutral pH) compares favourably with the d.p.a.s.v. technique at a rotating disk electrode (at low pH) because of the shorter collection period and greater sensitivity. 相似文献
15.
M. P. Shurygina S. A. Chesnokov M. A. Lopatin V. K. Cherkasov G. A. Abakumov 《Russian Chemical Bulletin》2004,53(11):2485-2489
A study of the kinetics of photoreduction of 9,10-phenanthrenequinone in the presence of hydrogen donors (para-substituted N,N-dimethylanilines and polymethylbenzenes) showed that plots of the quantum yield of photoreduction (H) and apparent reaction rate constant (k
H) vs. oxidation potential of hydrogen donors are extreme. In the presence of amines, k
H and H increase, as a whole, whereas they decrease in the presence of polymethylbenzenes. In coordinates H-G
e (G
e is the change in the free energy of electron transfer) for pairs quinone-H donor, H increases with G
e approaching to zero. For the amine series, this effect is mainly in the exothermic region of G
e (G
e < 0). For the series of polymethylbenzenes, this increase is observed in the endothermic region (G
e > 0).__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2381–2385, November, 2004. 相似文献
16.
G. V. Gridunova V. E. Shklover Yu. T. Struchkov E. N. Sidorenko A. M. Andrievskii Z. I. Ezhkova K. M. Dyumaev 《Russian Chemical Bulletin》1986,35(6):1163-1168
Conclusions An x-ray diffraction structural analysis established the molecular and crystal structure of the benzene solvate of 2,4,7-trinitro-9,10-phenanthrenequinone. The bond length distribution in this trinitrophenanthrenequinone indicates -electron localization at the periphery of the phenanthrenequinone system, whose significant distortion is due to steric and electronic factors.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1284–1290, June, 1986. 相似文献
17.
《Journal of Inorganic and Nuclear Chemistry》1981,43(9):2171-2173
A study of the air oxidation of 4-methyl catechol catalyzed by simple copper-amine complexes was performed in aqueous solutions at pH = 6.5. Simple bi-, tri- and tetra-nitrogen ligands were complexed to Cu2+ ions. Initial rate kinetics of their catalytic oxidation of 4-methyl catechol was followed optically. Proton NMR linebroadening and optical spectral studies were performed on the Cu2+-amine-catechol solutions and these spectral data were correlated with the kinetic studies. 相似文献
18.
The kinetics of the oxidation of catechol by aqueous copper(II) have been studied as a function of reactant concentrations at pH 6.4-7.2. To follow the reaction, a spectrophotometric method has been developed that circumvents the problem of precipitation of decomposition products of the initial o-quinone oxidation product. The rate law shows that the reactive species is the monocatecholate complex of Cu(II), and that this species undergoes rate-limiting intramolecular electron transfer with k = 1.9 x 10(-5) s(-1) (22 +/- 1 degrees C, mu = 0.125 M NaClO(4)). The results have allowed a reanalysis of previous work on the autoxidation in the aqueous Cu(II)-catechol-dioxygen system, and comparisons to mechanisms of copper(II) oxidases. 相似文献
19.
20.
Linko R. V. Belsky V. K. Varlamov A. V. Zaitsev B. E. Chernyshev A. I. 《Russian Chemical Bulletin》2001,50(9):1625-1629
The addition of acetone to 9,10-phenanthrenequinone and 2-nitro-, 2,7-dinitro-, and 2,4,7-trinitro-9,10-phenanthrenequinones in the presence of Al2O3 affords mono- and bisadducts. The crystal structures of 10-hydroxy-10-(2-oxopropyl)-2-nitro-9,10-dihydrophenanthren-9-one and 9,10:10,9-bishemiketal of 9,10-dihydroxy-2-nitro-9,10-bis(2-oxopropyl)-9,10-dihydrophenanthrene were determined. 相似文献