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1.
O. V. Sizova A. I. Panin V. I. Baranovskii N. V. Ivanova 《Journal of Structural Chemistry》1996,37(2):181-191
Semiempirical INDO-E/S+RCIP calculations of the electronic structures of the ground and excited states of the pyrazine (pz)
molecule and [Ru(NH3)5pz]q (q=+1, +2, +3) complexes were performed to analyze the dependence of the calculation results on the active MO space and configuration
basis set. Recommendations for the construction of the {Фk} basis sets and formation of the {ϕk} sets are given.
St. Petersburg State University. Translated fromZhurnal Struktumoi Khimii, Vol. 37, No. 2, pp. 206–219, March–April, 1996.
Translated by I. Izvekova 相似文献
2.
O. V. Sizova N. V. Ivanova V. I. Baranovskii A. B. Nikolskii 《Journal of Structural Chemistry》1994,35(4):433-442
The electronic structure and spectra of [Ru(NH3)5pyz]2+ and [(NH3)5Ru-pyz-Ru(NH3)5]4+ are calculated by the INDO (CINDO-E/S) method. Changes in molecular orbitals, charge distributions, and bond order indices
of the pyrazine molecule and [Ru(NH3)5pyz]2+ complex in the [(NH3)5Ru-pyz-Ru(NH3)5]4+ binuclear complex are analyzed.
St. Petersburg State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 4, pp. 12–23, July–August, 1994.
Translated by. O. Kharlamova 相似文献
3.
O. V. Sizova V. I. Baranovskii A. I. Panin N. V. Ivanova 《Journal of Structural Chemistry》1998,39(4):471-479
The dynamics of the intramolecular electron transfer from Ru(II) to Ru(III) in binuclear mixedvalence complexes [(NH3)5Ru-L- Ru(NH3)5]5+ (L = N2,pyz, bipy, pym, bpa) is analyzed by the semiempirical CINDO +CI method.
Translated fromZhumal Strukturnoi Khimii, Vol. 39, No. 4, pp. 579–590, July–August, 1998. 相似文献
4.
O. V. Sizova A. I. Panin N. V. Ivanova V. I. Baranovskii 《Journal of Structural Chemistry》1997,38(3):366-374
The electronic structure of the ground and excited states of the binuclear mixed-valence complex [Ru(NH3)5]2(4,4’-bipy)5+ is calculated by the semiempirical INDO + CI method, and an electronic spectrum assignment is given. A theoretical model
of electron transfer between the Ru(II) and Ru(III) metal centers is constructed on the basis of many-electron wave functions.
The dependence of the electron transfer characteristics on the angles between the planes of the pyridine rings and also between
the pyridine rings and the planes of cis(NH3)-Ru-cis(NH3) is analyzed.
Translated fromZhumal Struktumoi Khimii, Vol. 38, No. 3, pp. 447–456, May–June, 1997. 相似文献
5.
F. Muriel R. de la Vega F. Snchez R. Jimnez R. Prado‐Gotor F. Prez P. Prez‐Tejeda 《国际化学动力学杂志》2005,37(2):81-89
The kinetics of electron transfer reactions between [Fe(CN)6]4? and [Co(NH3)5pz]3+ and between [Ru(NH3)5pz]2+ and [Co(C2O4)3]3? was studied in concentrated salt solutions (Na2SO4, LiNO3, and Ca(NO3)2). An analysis of the experimental kinetic data, kobs, permits us to obtain the true (unimolecular) electron transfer rate constants corresponding to the true electron transfer process (precursor complex → successor complex), ket. The variations of both, kobs and ket, with salt concentrations are opposite for these reactions. These opposite tendencies can be rationalized by using the Marcus–Hush treatment for electron transfer reactions. The conclusion is that the negative salt effect found for the first reaction ([Fe(CN)6]4? + [Co(NH3)5pz]3+) is due to the increase of the reaction and reorganization free energies when the concentration of salt increases. In the case of the second reaction ([Ru(NH3)5pz]2+ + [Co(C2O4)3]3?), the positive salt effect observed is caused by the fact that the driving force becomes more favorable when the concentration of salt increases. Thus, it is shown that for anion/cation electron transfer reactions the kinetic salt effect depends on the charge sign of the oxidant (and the reductant). © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 37: 81–89, 2005 相似文献
6.
Wen-J. Mei Yu-Z. Ma Jie Liu Jin-C. Chen Kang-C. Zheng Liang-N. Ji Jun-H. Yao 《Transition Metal Chemistry》2006,31(3):277-285
A series of ruthenium(II) complexes with electron-donor or electron-acceptor groups in intercalative ligands, [Ru(phen)2(o-MOP)]2+ (1), [Ru(phen)2(o-MP)]2+ (2), [Ru(phen)2(o-CP)]2+ (3) and [Ru(phen)2(o-NP)]2+ (4), have been synthesized and characterized by elementary analysis, ES-MS, 1H NMR, electronic absorption and emission spectra. The binding properties of these complexes to CT-DNA have been investigated
by spectroscopy and viscosity experiments. The results showed that these complexes bind to DNA in intercalation mode and their
intrinsic binding constants (Kb) are 1.1, 0.35, 0.53 and 1.7 × 105 M−1, respectively. The subtle but detectable differences occurred in the DNA-binding properties of these complexes are mainly
ascribed to the electron-withdrawing abilities of substituents (–OCH3 < –CH3 < –Cl < –NO2) on the intercalative ligands as well as the intramolecular H-bond (for substituent –OCH3) which increase the planarity area of the intercalative ligand to some extent. The density functional theory (DFT) calculations
were also performed and used to further discuss the trend in the DNA-binding affinities of these complexes. 相似文献
7.
O. V. Sizova A. I. Panin V. I. Baranovskii N. V. Ivanova 《Journal of Structural Chemistry》1996,37(2):171-180
Semiempirical INDO-E/S calculations of [RuX6]q (X=NH3, q=+2, +3; X=CN−, q=−4, −3) complexes are performed to demonstrate that the MO relaxation in the electronically excited state can be taken
into account by introducing certain double excitations into the configuration interaction matrix; the principles of selection
of the excitations are discussed. The calculation results are compared with the experimental electronic absorption spectra.
St. Petersburg State University. Translated fromZhurnal Struktumoi Khimii, Vol. 37, No. 2, pp. 195–205, March–April, 1996.
Translated by I. Izvekova 相似文献
8.
Geometrical structures of nitroso complexes trans- [Ru(NO)(NH3)4(Cl)]2+, trans-[Ru(NO)(NH3)4(H2O)]3+, [Ru(NO)(Cyclam)(Cl)]2+(Cyclam is 1,4,8,11-tetraazocyclodecane), and [Ru(NO)(Bipy)2(Cl)]2+ (Bipy is 2,2-bipyridine) are optimized using the density functional method. The potential energy surface of all four complexes was found to contain local minima corresponding to a stable state with the 1-coordination of NO through the N atom and to two metastable isomers with the 1-O and 2-NO coordination. For [Ru(NO)Cl5)]2-, trans-[Ru(NO)(NH3)4(Cl)]2+, and trans-[Ru(NO)(NH3)4(H2O)]3+, the lowest electronically excited triplet states are calculated, as well as the reduced complexes with one additional electron. It is shown that the electron excitation and reduction are accompanied by bending of the RuNO group with a substantial elongation of the Ru-O and N-O bonds, which makes this group unstable. These processes do not cause any significant changes in the metal or in the nitroso ligand oxidation states because of the electron density delocalization in the RuNO group.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 32–42.Original Russian Text Copyright © 2005 by Sizova, Lubimova. 相似文献
9.
A. A. Kamyshova A. Z. Kreindlin M. I. Rybinskaya P. V. Petrovskii 《Russian Chemical Bulletin》2000,49(3):520-525
The reaction of decamethylruthenocene with oleum or with an oleum—acid (CF3SO3H or CF3CO2H) mixture as well as UV photolysis of a Cp*
2Ru solution in CF3SO3H in the presence of a small amount of oleum afforded two metallonium dications,viz., [Ru(η5-C5Me5)(η5:σ:σ-C5Me3(CH2)2]2+ and [Ru(H2)(η5:σ:-C5Me4CH2)2]2+. The structures of these dications were confirmed by the results of their alkaline hydrolysis and NMR spectra.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 517–522, March, 2000. 相似文献
10.
Prithwiraj Byabartta 《Journal of Chemical Sciences》2006,118(2):171-177
The reaction of ctc-[Ru(R-aapm)2Cl2] (1) with (NH4)2MoS2 in aqueous MeOH afforded redviolet mixed ligand complexes of the type [(R-aapm)2Ru(μ-S)2Mo(OH)2] (2a-2e) [R-aapm = 2-(arylazo) pyrimidine,p-R-C6H4-N=N-C4H3NN, R = H (2a), Me (2b), Cl (2c), OMe (2d), NO2 (2e)]. In complexes (2a-2e) the terminal Mo=S bonds of the MoS unit get hydroxylated and the molybdenum ion is reduced from the starting MoVI in MoS to MoIV in the final product. The solution electronic spectra ex-hibit a strong MLCT band at 550–570 nm in DCM. The1H NMR spectra confirms the geometry of the complexes as being that ofcistranscis isomers. Cyclic voltammograms show a Ru(III)/Ru(II) couple at 1.10–1-4 V, irreversible Mo(IV)/Mo(V) oxidations in the 1.66–1.72
V range, along with four successive reversible ligand reductions in the range -0.45–0.67 V (one electron), -0.82–1.12 V (one
electron),-1.44–1.90 V (simultaneously two electrons). 相似文献
11.
P. Perez‐Tejeda A. Jimenez‐Ruiz E. M. Grueso R. Prado‐Gotor C. Carrasco A. Pastor N. Alvarez M. Garcia‐Lora M. Garcia‐Pageo 《国际化学动力学杂志》2013,45(12):780-786
The electron transfer reaction between [Ru(NH3)5pz]2+ and [Co(C2O4)3]3? was studied in the presence of monomers and aggregates of bile salts (sodium deoxycholate, sodium taurodeoxycholate, and sodium glycocholate) at 298.2 ± 0.1 K. The results show a decreasing rate constant with the successive addition of bile salts. To rationalize the trends of the reaction rate on the [bile salts], two models were used. One of them takes into account the aggregation feature by considering a stepwise self‐association between monomers, whereas the other assumes the formation of a critical micellar concentration. Binding constants between [Ru(NH3)5pz]2+ species and deoxycholate or taurodeoxycholate aggregates were higher than that for glycocholate aggregates. These results are consistent with the way in which the monomers are added to form the bile anion aggregates. 相似文献
12.
Nizam M. El-Ashgar Issa M. El-Nahhal Mohamed M. Chehimi Michel Delamar Florence Babonneau Jacques Livage 《Journal of Sol-Gel Science and Technology》2007,41(1):3-10
A new insoluble solid functionalized ligand system bearing chelating ligand group of the general formula P-(CH2)3-N[CH2CONH(C6H4)NH2]2, where P represents [Si–O]
n
polysiloxane network, was prepared by the reaction of the immobilized diethyliminodiacetate polysiloxane ligand system, P-(CH2)3N(CH2CO2Et)2 with 1,2-diaminobenzene in toluene. 13C CP-MAS NMR, XPS and FTIR results showed that most ethylacetate groups (–COOEt) were converted into the amide groups (–N–C=O).
The new functionalized ligand system exhibits high capacity for extraction and removal of the metal ions (Fe3+, Co2+, Ni2+, Cu2+ and Zn2+) with efficiency of 95–97% after recovery from its primary metal complexes. This functionalized ligand system formed 1:1
metal to ligand complexes. 相似文献
13.
The structure of the product formed on boiling [RuNO(NH3)3(NO2)(OH)]Cl·0.5H2O in 3 M HNO3 is determined by XRD. The crystals belong to monoclinic symmetry. Crystallographic data for H11ClN6O8Ru are: a = 13.7924(4) ?, b = 6.9114(2) ?, c = 12.3577(4) ?, β = 111.863(1)°, V = 1093.27(6) ?3, Z = 4, d
calc = 2.185 g/cm3, space group Cc. The structure is built of complex [RuNO(NH3)3(H2O)Cl]2+ cations and NO3− anions. The compound is studied by IR spectroscopy and X-ray phase analysis.
Original Russian Text Copyright ? 2009 by V. A. Emel’yanov, E. V. Kabin, and I. A. Baidina
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 598–601, May–June, 2009. 相似文献
14.
S. A. Martynova K. V. Yusenko I. V. Korolkov I. A. Baidina S. V. Korenev 《Journal of Structural Chemistry》2009,50(1):120-126
Binary complex salts [Ru(NH3)5Cl][ReCl6] and [Ru(NH3)5Cl]2[ReCl6]Cl2 were synthesized and characterized. An X-ray diffraction analysis showed that they were isostructural with the previously
obtained isoformula salts [Rh(NH3)5Cl][OsCl6] and [Ir(NH3)5Cl]2[PtCl6]Cl2, respectively. Thermolysis of these compounds under hydrogen and helium was studied. According to X-ray phase analysis data,
bimetallic solid solutions Ru0.67Re0.33 and Ru0.50Re0.50 were the final products of thermolysis. Their unit cell parameters correspond to the characteristics of alloys with similar
compositions.
Original Russian Text Copyright ? 2009 by S. A. Martynova, K. V. Yusenko, I. V. Korolkov, I. A. Baidina, and S. V. Korenev
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 1, pp. 126–132, January–February, 2009. 相似文献
15.
Juribašić M Bellotto L Traldi P Tušek-Božić L 《Journal of the American Society for Mass Spectrometry》2011,22(10):1815-1825
The mass spectrometric behavior of palladium(II) halide complexes of three types of quinolinylaminophosphonates, diethyl and
dibutyl esters of [α-anilino-(quinolin-2-yl)methyl]phosphonic (L1, L2), [α-anilino-(quinolin-3-yl)methyl]phosphonic (L3, L4), and [α-(quinolin-3-ylamino)-N-benzyl]phosphonic acid (L5, L6), was investigated under positive ion electrospray ionization conditions. Each type of ligand forms complexes with different
metal–ligand interactions. Mononuclear dihalide adducts cis-[Pd(L1/L2)X2] (1–4) and trans-[Pd(L3/L4)2X2] (5–8) as well as dinuclear tetrahalide complexes [Pd2(L5/L6)3X4] (9–12) (X = Cl, Br) are formed by metal bonding either through the quinoline or both the quinoline and amino nitrogen atoms. The
sodiated molecule [M + Na]+ is observed in the mass spectra of all the complexes, and its abundance as well as the fragmentation pathway depend on the
type of the complex. In the cis complexes (1–4) the initial decomposition goes under two fragmentation routes: those in which the sodium molecular adduct sequentially loses
halides HX/NaX and those in which this loss is in the competition with the loss of dialkyl phosphite. The predominant pathways
for decomposition of trans dihalide (5–8) and tetrahalide (9–12) complexes include three competitive reactions; the loss of halides, dialkyl phosphites and the intact phosphonate ligand
molecule and its fragments formed by ester dissociation or complete loss of the phosphonate ester moiety. A series of acetonitrile
adducts and cluster ions derived from dimolecular clusters [2M + Na]+ were also detected. The most important fragmentation patterns are rationalized and supported by the MS
n
studies. 相似文献
16.
S. Vidhisha Kotha Laxma Reddy K. Ashwini Kumar Yata Praveen Kumar S. Satyanarayana 《Transition Metal Chemistry》2010,35(8):1027-1034
This article describes the synthesis of a polypyridyl ligand, namely 2-(2, 5-dimethoxyphenyl)-1H-imidazo[4,5-f]1,10-phenanthroline (DMPIP) and its Ru(II) complexes, namely [Ru(bipy)2DMPIP]2+ (1), [Ru(dmb)2DMPIP]2+ (2) and [Ru(phen)2DMPIP]2+ (3) ((bipy = 2,2′-bipyridine, dmb = 4,4′-dimethyl-2,2′-bipyridine, phen = 1,10-phenanthroline). The complexes were characterized
by elemental analysis, plus IR, 1H-NMR and 13C [1H]-NMR spectra. The interactions of the complexes with calf thymus DNA were investigated. The results indicate that the three
complexes can intercalate into DNA. Under irradiation at 365 nm, all three complexes promote the photocleavage of plasmid
pBR 322 DNA. Inhibitor studies suggest that singlet oxygen plays a significant role in the cleavage mechanism for the complexes. 相似文献
17.
O. V. Sizova N. V. Ivanova O. O. Lyubimova V. V. Sizov 《Russian Journal of Coordination Chemistry》2007,33(7):523-529
The B3LYP method in the LanL2DZ basis set was used to carry out geometry optimization for the binuclear bridged complexes [RuCl4(NO)(μ-Pyz)Ru(P)(CO)]?, [Ru(Bipy)2(NO)(μ-Pyz)Ru(NH3)5]5+, and [(NC)Ru(Py)4(μ-CN)Ru(Py)4NO]3+ (Pyz is pyrazine). The electronic spectra of the complexes were calculated by the TDDFT and CINDO-CI methods with allowance for solvation effects. The ground-state electronic configurations of the two ruthenium atoms in these compounds were shown to be different. Among the lower excited states of all complexes, states with essentially weakened Ru-NO bonds were found. The strong absorption in the visible region of the spectrum of [Ru(Py)4NO-CN-Ru(Py)4CN]3+ is due to the interfragment electron transfer RuII → {RuNO} accompanied by weakening of the bond between nitrogen oxide and the complex. 相似文献
18.
A dependence between the quadrupole coupling constants (e
2
Qq
zz
) and the asymmetry parameters of the electric field gradient (η) for the antimony atoms in the complex [SbF5]2− anions of M2SbF5 pentafluoroantimonites (M=Na, K, Rb, Cs, NH4, Ti, and Et2NH2) was revealed from the123Sb NQR spectra at 77 K.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1988–1990, October, 1998. 相似文献
19.
İbrahim Erden Ali Erdoğmuş Nebahat Demirhan Ulvi Avcıata 《Transition Metal Chemistry》2008,33(4):439-442
A new fluorene ligand, benzo[15-crown-5]-5H-pyrido[3′,2′:4,5]cylopenta[1,2-b]pyridin-5-ylidenehydrazone (bph), has been synthesized from the reaction of 4,5-diazafluoren-9-one
with 4′-formylbenzo-15-crown-5. The Co(II), Cu(II), and Ru(II) complexes of the ligand were prepared and characterized. The
metal-to-ligand ratio of the Co(II) and Cu(II) complexes was found to be 2:1 and that of the Ru(II) complex was found to be
1:1. The ligand and complexes have been characterized by FTIR, UV–visible, 1H NMR and fluorescence spectra, as well as elemental analyses and mass spectra. 相似文献
20.
A simple method of localizing molecular orbitals on polyatomic molecular fragments is proposed; the method allows one to separate
orbitals in the structural units of extended molecules. The method is illustrated by semiempirical calculations of the binuclear
bridged complexes [(NH3)5Rupy-(C2H2)n-py-Ru(NH3)5]5+ (n = 0,1,2,3). One of possible application is construction of orbital bases for calculations by the configuration interaction
method with limited sets of active MOs.
Translated fromZhumal Strukturnoi Khimii, Vol. 39, No. 4, pp. 571–578, July–August, 1998. 相似文献