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11.
Patra S Sarkar B Ghumaan S Patil MP Mobin SM Sunoj RB Kaim W Lahiri GK 《Dalton transactions (Cambridge, England : 2003)》2005,(7):1188-1194
The isomeric title complexes were obtained in almost equimolar ratio from the reaction of Ru(trpy)Cl3 and L. Crystal structure analyses of the perchlorate hemihydrates, electrochemical and spectroscopic (NMR, UV/VIS, EPR) studies, supported by DFT calculations, reveal distinct differences between the isomeric redox series [1]n+(tetrazine-Nt trans to Cl) and [2]n+(pyrazolyl-Np trans to Cl; n= 0, 1, 2). The latter system with the pi acceptors trpy and tetrazine in the equatorial plane and the pyrazolyl and chloride donors in the axial positions exhibits facilitated oxidation, lower energy MLCT transitions, more balanced chelate coordination, and a higher g anisotropy in the oxidised (RuIII) state. According to partially resolved EPR spectra of one-electron reduced neutral compounds and they have the unpaired electron predominantly in the tetrazine ring of L. 相似文献
12.
13.
Rita Das Nigamananda Das Anadi C. Dash Ansuman Roy Shyamal K. Sarkar 《Transition Metal Chemistry》1996,21(1):90-94
Summary The reaction of ()-(tetren)CoOH2+ with S2O
3
2-
in the 7.25–8.28 pH range at 20–40 °C yielded S- (yellow) and O- (purple) bonded thiosulfato(tetren)cobalt(III) complexes, the former in larger quantities. The rate determining step is preceded by diffusion-controlled ion-pair [(tetren)CoOH2+,S2O
3
2-
] formation. Replacement of coordinated OH- by S2O
3
2-
is interpreted in terms of an internal conjugate base mechanism: (tetren)CoOH2+ (tetren-H)CoOH
2
2+
, the reactive amido conjugate base being generated by intramolecular proton transfer from the coordinated NH site.In acid medium the S-bonded (tetren)Co(S2O3)+ is highly stable to redox decomposition, in contrast to its pentaammine analogue. The complex however, undergoes base hydrolysis yielding the corresponding hydroxo complex. The rate and activation parameters for the base hydrolysis have been reported. Photolysis of O- and S-bonded isomers of [(tetren)CoS2O3]+ in acidic medium at 254 and 313 nm, respectively, yielded aquation products accompanied by some decomposition of S2O
3
2-
. 相似文献
14.
15.
16.
Arun K. Sinha Vinod Kumar Abhishek Sharma Anuj Sharma Rakesh Kumar 《Tetrahedron》2007,63(45):11070-11077
A mild and convenient one-pot two-step synthesis of hydroxystilbenes with trans selectivity has been developed through a modified Perkin reaction between benzaldehydes and phenylacetic acids bearing 4- or 2-hydroxy substitution at the aromatic ring, in the presence of piperidine-methylimidazole and polyethylene glycol under microwave irradiation. The observation of a simultaneous condensation-decarboxylation leading to the unusual formation of hydroxystilbenes in lieu of α-phenylcinnamic acid reveals an interesting facet to the classical Perkin reaction. The developed protocol provides a green alternative to the prevalent methods employing a toxic decarboxylating agent in the form of quinoline/Cu salt, and the requirement for harsh protection-deprotection steps for the synthesis of hydroxylated stilbenes. 相似文献
17.
Polygonal (mainly triangular) silver nanoprisms were prepared by reducing silver perchlorate in formamide in the presence of polyethylene glycol (PEG) at room temperature. The reduction of silver ions by formamide leads to the deposition of arrays of triangular shaped silver nanoparticles on the glass walls of the container, accompanied by evolution of CO2 gas. In the presence of poly(N-vinyl-2-pyrrolidone) (PVP) and PEG (1:1), both nanospheres and nanoprisms are formed. 相似文献
18.
Sarkar B Kaim W Klein A Schwederski B Fiedler J Duboc-Toia C Lahiri GK 《Inorganic chemistry》2003,42(20):6172-6174
The Ru(2)(III,II) mixed-valent state is strongly stabilized in [(bpy)(2)Ru(mu-bttz)Ru(bpy)(2)](5+) (3(5+), bttz = 3,6-bis(2-thienyl)-1,2,4,5-tetrazine, as evident from lowered oxidation potentials and isolability, a strongly increased comproportionation constant K(c) = 10(16.6), and a high-energy intervalence charge transfer band at 10100 cm(-1). Curiously, no such effects were observed for the diosmium(III,II) analogue, whereas the related systems [(bpy)(2)M(mu-bmptz)M(bpy)(2)](5+), bmptz = 3,6-bis(4-methyl-2-pyridyl)-1,2,4,5-tetrazine, exhibit conventional behavior, i.e., a slightly higher K(c) value of the Os(2)(III,II) analogue. EPR signals were observed at 4 K for 3(5+) but not for the other mixed-valent species, and high-frequency (285 GHz) EPR was employed to study the diruthenium(II) radical complexes 2(3+) and 3(3+). 相似文献
19.
The metal ion (M2+) catalysed dissociation of cis-diaquobisoxalatochromate into the tetraaquomonooxalato complex in aqueous perchloric acid medium which follows the rate law — d(complex)/dt = {kH[H+] + kM[M2+]}[complex] has been studied. Based on kM values the order of catalysing effect of the different metal ions studied is Cu2+ > Ni2+ > Co2+ > Mn2+, which is also the order of stabilities (KMOx) of the monooxalato complexes of these metal ions; in fact the plot of log kM vs. log KMOx is linear. This together with the relative values of ΔH≠ and ΔS≠ for the H+ catalysed and M2+ catalysed paths is in agreement with a mechanism involving chelation of the catalysing cation through the free carbonyl oxygens of the oxalate ligand bound to Cr(III), followed by the dissociation of the Cr(III)? O bonds with simultaneous entry of two water molecules into the coordination sphere of Cr(III). 相似文献
20.
S. R. Sarkar K. Une Y. Tominaga 《Journal of Radioanalytical and Nuclear Chemistry》1997,220(2):155-159
This work reports the determination of oxygen to uranium (O/U) ratio in irradiated UO2+x fuel pellet of burnup of ca. 34 GWd/t by controlled potential coulometry. The method is based on the dissolution of the nuclear fuel in strong phosphoric acid (SPA) at 180–190 °C under an inert atmosphere. After dissolution, 8% sulphuric acid is added in order to obtain a 20% SPA in 8% sulphuric acid. A controlled potential coulometric determination of uranium(VI) is carried out at ?0.60V vs. ferri-ferrocyanide. The uranium(IV) contained in an aliquot of the fuel solution is oxidised to uranium(VI) with cerium(IV) sulphate, and the total uranium content is then determined by coulometry. Optimum experimental conditions have been established using simulated irradiated fuel solution containing various fission products which include cerium, tellurium, palladium, ruthenium, molybdenum and zirconium. Interference of the fission products and the possible removal of their interferences by preelectrolysis at +0.5 V vs. saturated calomel electrode (SCE) have been investigated. The accuracy of the coulometric method is confimed by polarographic measurement using several unirradiated UO2+x fuel of known stoichiometry. 相似文献