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1.
Dechlorination of Ru(PPh3)2(TaiMe)Cl2 (TaiMe = p-Me-C6H4-N=N-C3H2NN(1)-Me (1), 1-methyl-2-(p-tolylazo)imidazole) has been carried out in acetone solution by Ag+ and reacted with N,N’-chelators to synthesise [Ru(PPh3)2 (TaiMe)(N,N’)]2+. The complexes have been isolated as their perchlorate salts. The N,N’ chelators are 1-alkyl-2-(phenylazo)imidazoles (PaiX,
X = Me, Et, CH2Ph); 2-(arylazo)pyridines, (Raap,p-R-C6H4-N=N-C5H4N; R = H, Me, Cl); 2-(arylazo)pyrimidines (Raapm,p-R-C6H4-N=N-C3N2H2; R = H, Me, Cl); 2,2’-bipyridine (bpy) and 1,10-phenanthroline (o-phen). Unsymmetrical N,N’ chelators may give two isomers
and this is indeed observed. The1H NMR spectral data refer to the presence of two isomers in the mixture in different proportions. With consideration of coordination
pairs in the order of PPh3, PPh3; N,N (N refers to N(immidazole)) and N’,N (N’ refers to N(azo)), the complexes have been characterised astrans-cis-cis andtrans-trans-trans configuration; the former predominates in the mixture. Electrochemical studies exhibit high potential Ru(III)/Ru(II) couple
and quasireversible N=N reduction. Electronic spectra show high intensity (ε ∼ 104) MLCT transition in the visible region (520 ±10) nm along with a shoulder (ε ∼ 103) in the longer wavelength region. 相似文献
2.
Amitava Dutta Mahammad Ali Sumana Gangopadhyay Pradyot Banerjee 《Journal of Chemical Sciences》1994,106(4):881-886
The electron transfer reactions of Mo(CN)8
4, W(CN)8
4− and Fe(CN)6
4− with the manganese (III) complex oftrans-cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetic acid have been studied by stopped-flow spectrophotometry in the pH range 2.0–6.5.
Analysis of kinetic data conforms to an outer-sphere process in each case. The validity of Marcus’ crossreaction relation
to these reactions is fairly satisfactory. 相似文献
3.
P. Byabartta 《Russian Journal of Coordination Chemistry》2009,35(9):687-691
Silver-assisted aquation of blue cis-trans-cis-RuCl2(RAaiR’)2 (I) leads to the synthesis of solvento species, blue-violet cis-trans-cis-[Ru(OH2)2(RAaiR’)2](ClO4)2 (II), where RAaiR’ = p-R-C6H4-N=N-C3H2-NN, abbreviated as N,N′ chelator (N(imidazole) and N(azo) represent N and N′, respectively); R = H (a), p-Me (b), p-Cl(c); R′ = Me (III), Et (IV), Bz (V), that reacted with NCS− in warm EtOH resulting in red-violet dithiocyanato complexes of the type [Ru(NCS)2(RAaiR)2] (IIIa–Vn). These complexes were studied by elemental analysis, UV-Vis, IR, and 1H NMR spectroscopy and cyclic voltammetry. The solution structure and stereoretentive transformation in each step have been
established from 1H NMR results. All the complexes exhibit strong MLCT transitions in the visible region. They are redox active and display
one metal-centered oxidation and successive ligand-based reductions. Linkage isomerisation was studied by changing the solvent
and then by UV-Vis spectral analysis. 相似文献
4.
Galactose oxidase (GOase) is a fungal enzyme which is unusual among metalloenzymes in appearing to catalyse the two electron
oxidation of primary alcohols to aldehydes and H2O2. The crystal structure of the enzyme reveals that the coordination geometry of mononuclear copper(II) ion is square pyramidal,
with two histidine imidazoles, a tyrosinate, and either H2O (pH 7.0) or acetate (from buffer,pH 4-5) in the equatorial sites and a tyrosinate ligand weakly bound in the axial position. This paper summarizes the results
of our studies on the structure, spectral and redox properties of certain novel models for the active site of the inactive
form of GOase. The monophenolato Cu(II) complexes of the type [Cu(L1)X][H(L1) = 2-(bis(pyrid-2-ylmethyl)aminomethyl)-4-nitrophenol and X− = Cl−
1, NCS−
2, CH3COO−
3, ClO4
−
4] reveal a distorted square pyramidal geometry around Cu(II) with an unusual axial coordination of phenolate moiety. The coordination
geometry of 3 is reminiscent of the active site of GOase with an axial phenolate and equatorial CH3COO− ligands. All the present complexes exhibit several electronic and EPR spectral features which are also similar to the enzyme.
Further, to establish the structural and spectroscopic consequences of the coordination of two tyrosinates in GOase enzyme,
we studied the monomeric copper(II) complexes containing two phenolates and imidazole/pyridine donors as closer structural
models for GOase. N,N-dimethylethylenediamine and N,N’-dimethylethylenediamine have been used as starting materials to obtain
a variety of 2,4-disubstituted phenolate ligands. The X-ray crystal structures of the complexes [Cu(L5)(py)], (8) [H2(L5) = N,N-dimethyl-N’,N’-bis(2-hydroxy-4-nitrobenzyl) ethylenediamine, py = pyridine] and [Cu(L8)(H2O)] (11), [H2(L8) = N,N’-dimethyl-N,N’-bis(2-hydroxy-4-nitrobenzyl)ethylenediamine] reveal distorted square pyramidal geometries around Cu(II) with the axial tertiary
amine nitrogen and water coordination respectively. Interestingly, for the latter complex there are two different molecules
present in the same unit cell containing the methyl groups of the ethylenediamine fragmentcis to each other in one molecule andtrans to each other in the other. The ligand field and EPR spectra of the model complexes reveal square-based geometries even in
solution. The electrochemical and chemical means of generating novel radical species of the model complexes, analogous to
the active form of the enzyme is presently under investigation. 相似文献
5.
S. Durmuş Ü. Ergun J. C. Jaud K. C. Emregül H. Fuess O. Atakol 《Journal of Thermal Analysis and Calorimetry》2006,86(2):337-346
Ni(II)–M(II)–Ni(II) nuclear structured
complexes were prepared from N,N’-bis(salicylidene)-1,3-propanediamine
(LH2) and its derivatives N,N’-bis(salicylidene)-2,2’-dimethyl-1,3-propanediamine
(LDMH2) and N,N’-bis(salicylidene)-2-hydroxy-1,3-propanediamine
(LOH3), where M represents one of the following
metal ions; Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II). Two different
μ-bridges are found between the metal nucleus of the complexes. The
phenolic oxygens and acetate ions tend to form μ-bridges between the
terminal Ni(II) ions and central metal(II) ion. The coordinatively bonded
DMF molecules, in the complexes, were observed to abandon the structure between
160–180°C. Further heating resulted primarily in the thermal decomposition
of the complexes above 310°C, whereas metal oxide residue mixtures were
observed above 650°C. 相似文献
6.
E. V. Matveeva K. A. Lyssenko P. V. Petrovskii G. -V. R?shenthaler I. L. Odinets 《Russian Chemical Bulletin》2009,58(4):817-822
The Arbuzov reaction of N,N’-phenylenedibenzimidoyl dichlorides furnished new tetradentate ligands, viz., N,N’-bis[(diphenylphosphoryl)phenylmethylidene]benzenediamines, which form complexes with lanthanides. 相似文献
7.
Sushanta Saha Prodyut Kumar Sarkar Ambikesh Mahapatra 《Transition Metal Chemistry》2006,31(3):389-395
The reaction between Pd(N,N′)Cl2 [N,N′ ≡ 1-alkyl-2-(arylazo)imidazole (N,N′) and picolinic acid (picH) have been studied spectrophotometrically at λ = 463 nm in MeCN at 298 K. The product is [Pd(pic)2] which has been verified by the synthesis of the pure compound from Na2[PdCl4] and picH. The kinetics of the nucleophilic substitution reaction have been studied under pseudo-first-order conditions.
The reaction proceeds in a two-step-consecutive manner (A → B → C); each step follows first order kinetics with respect to
each complex and picH where the rate equations are: Rate 1 = {k′0 + k′2[picH]0} × [Pd(N,N′)Cl2] and Rate 2 = {k′′0 + k′′2[picH]0}[Pd(N,O)(monodentate N,N′)Cl2] such that the first step second order rate constant (k′2) is greater than the second step second order rate constant (k′′2). External addition of Cl− (as LiCl) suppresses the rate. Increase in π-acidity of the N,N′ ligand, increases the rate. The reaction has been studied
at different temperatures and the activation parameters (Δ‡H° and Δ‡S°) were calculated from the Eyring plot. 相似文献
8.
W. Görner O. Haase Chr. Segebade 《Journal of Radioanalytical and Nuclear Chemistry》2007,271(1):199-201
The extraction of uranyl nitrate by the novel extractant N,N’-dimethyl-N,N’-dioctylsuccinylamide (DMDOSA) from aqueous nitric/nitrate
solutions was investigated. The effects of concentration of HNO3 and DMDOSA on the U(VI) extraction distribution was studied. The extraction mechanism was established and the stoichiometry
of the main extracted species was confirmed to be UO2(NO3)2·2DMDOSA. The value of ΔH of the extraction is −23.9±1.7 kJ·mol−1. A IR spectral study of the U(VI) extracted species was also made. 相似文献
9.
Furong Xiao Lu Chen Jide Wang Ronglan Wu Fan Yue Jing Li 《Frontiers of Chemistry in China》2007,2(2):169-173
Three new cobalt complexes were synthesized by solid-state reaction at room temperature and the resultant Co complexes reacted
with two equivalent oxygen molecules at room temperature to produce the oxygenated complexes [Co·(L1)2·(O2)2](NO3)2·2H2O (L1 = N, N’-bis(4-hydroxyl-3-methoxy-benzyl)-diethylenetriamine), [Co·(L2)2·(O2)2](NO3)2·2H2O (L2 = N, N’-bis(4-hydroxyl-3-methoxy-benzyl)-triethylenetetramine), and [Co·(L3)2·(O2)2](NO3)2·2H2O (L3 = N, N’-bis(4-hydroxyl-3-methoxy-benzyl-tetraethylenepentamine). The oxygenated complexes were characterized by elemental
analysis, IR (Infrared), 1H-NMR (Nuclear Magnetic Resonance), and UV-Vis (Ultraviolet Visual) spectrometry, and TG/DTA (Thermogravimetry/Differential
Thermal Analysis) analysis, and molar conductance. The coordinated oxygen contents in the oxygenated complexes were also determined
by weight method. It was supposed that only one O2 molecule coordinated to the Co ion forming a superoxo type oxygenated complex.
Translated from Acta Chimica Sinica, 2006, 64(15): 1517–1522 (in Chinese) 相似文献
10.
J. Q. Gao T. Wu J. Wang X. D. Jin D. Li B. X. Wang K. Li Y. Li 《Russian Journal of Coordination Chemistry》2011,37(11):817-824
In this work, the title complexes, (EnH2)1.5[ErIII(Ttha)] · 3H2O (I) and (EnH2)[ErIII(Egta)(H2O)]2 · 6H2O (II), where En = ethylenediamine, H6Ttha = triethylenetetramine-N,N,N′,N″,N″’,N″′-hexaacetic acid, H4Egta = ethyleneglycol-bis-(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, have been successfully synthesized. Their structures have been characterized by IR spectroscopy and single-crystal
X-ray diffraction techniques. The X-ray diffraction reveals that I is nine-coordinated and crystallizes in the monoclinic crystal space group P2/n with cell dimensions a = 17.6058(16), b = 9.6249(9), c = 20.560(2) ?, β = 109.7440(10)°, and V = 3279.1(5) ?3. Compound II is also nine-coordinated and crystallizes in the monoclinic crystal space group P21/n with the cell dimensions a = 12.938(6), b = 12.651(5), c = 14.943(6) ?, β = 105.441(5)°, and V = 2357.5(17) ?3. In I, each EnH22+ cation connects three adjacent [ErIII(Egta)(H2O)]− complex anions through hydrogen bonds, while in I, there are two types of EnH2
2+ anions. One is highly symmetrical, forming hydrogen bonds with two neighboring [ErIII(Ttha)]3− complex anions. The other anion connects three adjacent [ErIII(Ttha)]3− complex anions through hydrogen bonds. These hydrogen bonds lead to the formation of 2D ladder-like layer structure. 相似文献
11.
Reaction of [Au2(dppm)Cl2] with AgOTf in CH2Cl2 medium followed ligand addition and leads to [Au2(dppm)(RaaiR′)](OTf) [RaaiR′ = p-R–C6H4–N = N–C3H2–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH2CH3
(2), CH2Ph (3), OSO2CF3 is the triflate anion, and dppm is the diphenylphosphinomethane-ring]. The 1H-n.m.r. spectral measurements suggest methylene, –CH2–, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets with coupling constant of avg. 6 Hz. Considering all the moities there are a lot of different
carbon atoms in the molecule which gives a lot of different peaks in the 13C-n.m.r spectrum. In the 1H–1H-COSY spectrum of the present complexes and contour peaks in the 1H–13C-HMQC spectrum in the present complexes, assign the solution structure and stereoretentive transformation in each step. 相似文献
12.
Reaction of [Ni(dppe)Cl2/Br2] with AgOTf in CH2Cl2 medium following ligand addition leads to [Ni(dppe)(OSO2CF3)2] and then [Ni(dppe)(RaaiR)](OSO2CF3)2 [RaaiR′ = p–R–C6H4–N=N–C3H2–NN-1–R′,(1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH2CH3
(2), CH2Ph (3), OSO2CF3 is the triflate anion]. 31P{1H}-NMR confirm that stable bis-chelated square planar Ni(II) azoimine–dppe complex formation with one sharp peaks. The 1H NMR spectral measurements suggest azoimine link is present with lot of phenyl protons in the aromatic region. Considering
all the moities there are a lot of different carbon atoms in the molecule which gives many different peaks in the 13C(1H)-NMR spectrum. In the 1H-1H COSY spectrum in the present complexes and contour peaks in the 1H-13C-HMQC spectrum in the present complexes, assign the solution structure and stereoretentive conformation in each complexes. 相似文献
13.
S. M. Kobelev A. D. Averin A. K. Buryak I. P. Beletskaya 《Russian Journal of Organic Chemistry》2010,46(8):1231-1242
Amination of a double excess of 4,6-dichloropyrimidine with various diamines in the presence of cesium carbonate in boiling
dioxane quantitatively afforded the corresponding N,N′-bis(6-chloropyrimidin-4-yl) derivatives, while its reactions with tri- and tetraamines gave N,N′,N″-tris- and N,N′,N″,N‴-tetrakis(6-chloropyrimidin-4-yl) derivatives. Equimolar amounts of 2,4-dichloro- or 4,6-dichloropyrimidine and diamines reacted
in the presence of Pd(0) complexes to form macrocyclic compounds containing pyrimidine fragments. Catalytic reactions of 4
equiv of diamines with 4,6-dichloropyrimidine can lead to the formation of 4,6-bis-(diamino)pyrimidines. Relations between
the yield and the nature of diamine and catalytic system were found. 相似文献
14.
Salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides, RCH(OH)CH2N(O)=NO− M+ (R=Me, Pri, or But; and M=Li, Na, K, Ag, NH4, or Me4N), were prepared. Their alkylation with alkyl halides R′X (X=Cl, Br, or I) and dimethyl sulfate was studied. Generally, alkylation
afforded mixtures ofN-(β-hydroxyalkyl)-N′-alkoxydiazeneN-oxides RCH(OH)CH2N(O)=NOR′ andO-alkyl-N-(β-hydroxyalkyl)-N-nitrosohydroxylamines RCH(OH)CH2N(NO)OR′.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1996–2001, October, 1998. 相似文献
15.
Prithwiraj Byabartta 《Transition Metal Chemistry》2007,32(8):1007-1011
Reaction of [Au(C6F5)(tht)2Cl](OTf) with RaaiR′ in CH2Cl2 medium leads to [Au(C6F5)(RaaiR′)Cl](OTf) [RaaiR′ = p-R–C6H4–N=N–C3H2–NN-1-R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH2CH3
(2), CH2Ph (3), tht is tetrahydrothiophen]. The maximum molecular peak of [Au(C6F5)(MeaaiMe)Cl] is observed at m/z 599.51 (100 %) in the FAB mass spectrum. Ir spectra of the complexes show –C=N– and –N=N– stretching near at 1590 and 1370 cm−1 and near at 1510, 955, 800 cm−1 due to the presence of pentafluorophenyl ring. The 1H-NMR spectral measurements suggest methylene, –CH2–, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph shows AB type quartets. 13C-NMR spectrum of complexes confirm the molecular skeleton. In the 1H-1H-COSY spectrum as well as contour peaks in the 1H-13C HMQC spectrum for the present complexes, assign the solution structure and stereoretentive conformation. The electrochemistry
gives the ligand reduction peaks. 相似文献
16.
The geometries of N,N′-diphenylbenzene-1,4-diamine (DPPD), N-phenyl-N′-(1-phenylethyl)benzene-1,4-diamine (SPPD), N-(4-methylpentan-2-yl)-N′-phenylbenzene-1,4-diamine (6PPD), N-propan-2-yl-N′-phenylbenzene-1,4-diamine (IPPD), N-(2-methoxybenzyl)-N′-phenylbenzene-1,4-diamine (MBPPD), and N-phenyl-N′-(2-phenylpropan-2-yl)benzene-1,4-diamine (CPPD) as well as of their dehydrogenation products were optimized by the semiempirical
AM1 method. The results support the idea of stable NB=CX structures formation during the consecutive dehydrogenation of SPPD, 6PPD, IPPD, and MBPPD antioxidants. The biradicals formed
during the second step of dehydrogenation of substituted phenylenediamines might be important for their antioxidant effectiveness.
Dedicated to Professor Vladimír Kvasnička, DrSc., in honour of his 65th birthday 相似文献
17.
M. Aksu S. Durmu M. Sari K. C. Emregül I. Svoboda H. Fuess O. Atakol 《Journal of Thermal Analysis and Calorimetry》2007,90(2):541-547
N,N′-bis(salicylidene)-1,3-propanediamine (LH2), N,N′-bis(salicylidene)-2,2′-dimethyl-1,3-propanediamine (LDMH2), N,N′-bis(salicylidene)-2-hydroxy-1,3-propanediamine (LOH3), N,N′-bis(2-hydroxyacetophenylidene)-1,3-propanediamine (LACH2) and N,N′-bis(2-hydroxyacetophenone)-2,2′-dimethyl-1,3-propanediamine (LACDMH2) were synthesized and reduced to their phenol-amine form in alcoholic media using NaBH4 (LHH2, LDMHH2, LOHHH2, LACHH2 and LACDMHH2). Heterodinuclear complexes were synthesized using Ni(II), Zn(II) and Cd(II) salts, according to the template method in DMF
media.
The complex structures were analyzed using elemental analysis, IR spectroscopy, and thermogravimetry. Suitable crystals of
only one complex were obtained and its structure determined using X-ray diffraction, NiLACH·CdBr2·DMF2, space group orthorhombic, Pbca, a=20.249, b=14.881, c=20.565 ? and Z=8. The heterodinuclear complexes were seen to be of [Ni·ligand·MX2·DMF2] structure (ligand=LH2−, LDMH2−, LOHH2−, LACH2−, LACDMH2−, M=ZnII, CdII, X=Br−, I−). Thermogravimetric analysis showed irreversible bond breakage of the coordinatively bonded DMF molecules followed by decomposition
at this temperature. 相似文献
18.
Robert W. Hay Norman Govan Angelo Perotti Oliviero Carugo 《Transition Metal Chemistry》1992,17(2):161-163
There has been considerable interest in the coordination chemistry of linear and macrocyclic amides(1). Deprotonation of the amide nitrogen is known to occur with various metal ions and the sites of coordination are generally
considered to be the carbonyl oxygen prior to deprotonation and the amide nitrogen after deprotonation. However, oxygen binding
has generally been inferred from indirect evidence(2,3). We now report the results of some studies on the interaction of copper(II) with a series of 2-carbamoylethyl derivatives
of linear diamines, namelyN,N′-bis(2-carbamoylethyl)ethylenediamine (1),N,N,N′,N′-tetrakis(2-carbamoylethyl)ethylenediamine (2)N,N′-bis(2-carbamoylethyl)trimethylenediamine (3) andN,N,N′,N′-tetrakis(2-carbamoylethyl)trimethylenediamine (4) which confirm carbonyl oxygen binding prior to amide deprotonation. 相似文献
19.
The title compound is the first example of N,N′-diethylnicotinamidium, [denaH]+, salt which has been characterized by X-ray analysis and IR spectra. [denaH]ClO4 was obtained from the reaction mixture prepared from N,N′-diethylnicotinamide (dena) and Fe(ClO4)3 in ethanol without any addition of HClO4. The proton required for protonation of dena is produced by hydrolysis of aquairon(III) cations. In the crystal structure,
cations and anions are held together by ionic interactions. The cations are linked to each other by pyridinium-carbonyl N-H⋯O=C
hydrogen bonds and an infinite linear chain along axis a is formed.
Dedicated to Professor Milan Melník on the occasion of his 70th birthday 相似文献
20.
V. V. Frolov A. G. Mazhuga E. K. Beloglazkina N. V. Zyk M. P. Egorov 《Russian Chemical Bulletin》2010,59(3):544-549
A method for the synthesis of new tetradentate organic ligand of the N2S2 type, viz., N,N’-bis-(2-mercaptophenyl)propane-1,3-diamine has been developed, starting from 2-( tert-butyl-thio)aniline and malonyl dichloride. Coordination compound of this ligand with NiII according to the X-ray diffraction data has a square-planar geometry of the metal ion coordination sphere. 相似文献