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61.
The apparent and limiting apparent molar volumes of dilute aqueous solutions of KBF4, and the complexes [Fe(DMSO)6](BF4)3, [Fe(Py)4(H2O)2](BF4)3, [Fe(4-Mepy)2(H2O)2](BF4)3, and [Fe(4-Etpy)2(H2O)2](BF4)3 were determined from density data measured at 5, 15, and 25°C. The apparent and limiting apparent molar adiabatic compressibilities of these complexes were determined from ultrasonic sound velocities measured at the same temperatures in dilute aqueous solutions. The volume change associated with complex formation is discussed in terms of the nature of the coordinate bond and also the role of the central metal atom and ligands in the solvation behavior of these complexes. 相似文献
62.
This article deals with isomeric ruthenium complexes [RuIII(LR)2(acac)] (S=1/2) involving unsymmetric β‐ketoiminates (AcNac) (LR=R‐AcNac, R=H ( 1 ), Cl ( 2 ), OMe ( 3 ); acac=acetylacetonate) [R=para‐substituents (H, Cl, OMe) of N‐bearing aryl group]. The isomeric identities of the complexes, cct (cis‐cis‐trans, blue, a ), ctc (cis‐trans‐cis, green, b ) and ccc (cis‐cis‐cis, pink, c ) with respect to oxygen (acac), oxygen (L) and nitrogen (L) donors, respectively, were authenticated by their single‐crystal X‐ray structures and spectroscopic/electrochemical features. One‐electron reversible oxidation and reduction processes of 1 – 3 led to the electronic formulations of [RuIII(L)(L ? )(acac)]+ and [RuII(L)2(acac)]? for 1 +‐ 3 + (S=1) and 1? – 3? (S=0), respectively. The triplet state of 1 +‐ 3 + was corroborated by its forbidden weak half‐field signal near g≈4.0 at 4 K, revealing the non‐innocent feature of L. Interestingly, among the three isomeric forms ( a – c in 1 – 3 ), the ctc ( b in 2 b or 3 b ) isomer selectively underwent oxidative functionalization at the central β‐carbon (C?H→C=O) of one of the L ligands in air, leading to the formation of diamagnetic [RuII(L)(L ′ )(acac)] (L ′ =diketoimine) in 4 / 4′ . Mechanistic aspects of the oxygenation process of AcNac in 2 b were also explored via kinetic and theoretical studies. 相似文献
63.
Dinda Soumitra Patra Sarat Chandra Panda Bikash Kumar Ganguly Sanjib 《Transition Metal Chemistry》2019,44(4):341-347
Transition Metal Chemistry - A pyridylhydrazone incorporating an anthracene moiety, designated as HLAnc, has been synthesized in order to examine its coordination behaviour towards rhodium(III).... 相似文献
64.
Reactions of OH radicals and some one-electron oxidants with 2-aminopyridine (2-AmPy) and 3-aminopyridine (3-AmPy) were studied in aqueous solutions using pulse radiolysis technique. The OH adduct of 2-AmPy at pH 9 has an absorption maximum at 360 nm along with a weak absorption band in the visible region and was found to be reactive with oxygen. The rate constant for its reaction with O2 was determined to be 1.0×108 dm3 mol−1 s−1. At pH 4 also, the OH adduct of 2-AmPy has an absorption band at 360 nm. However, there are differences in the absorption at other wavelengths. From the plot of ΔOD vs. pH at 340 nm, the pKa of the OH adduct was determined to be 6.5. Among the specific oxidants, only SO4−√ radicals were able to oxidize 2-AmPy. In the case of 3-aminopyridine (3-AmPy), the transient species formed by OH radical reaction at pH 9 has an absorption maximum at 410 nm with shoulder bands on both the sides. Its absorption spectrum at pH 4 was different indicating the existence of a pK value for the OH adduct. pKa of 3-AmPy-OH radical adduct species was evaluated to be 5.7. This adduct species was also found to be reactive with oxygen (k=7.6×106 dm3 mol−1 s−1). Specific one-electron oxidants like N3√, Br2−√ C2−√ and SO4−√ were able to oxidize 3-AmPy indicating that it is easier to oxidize 3-AmPy as compared to 2-AmPy. 相似文献
65.
Ballester P Capó M Costa A Deyà PM Frontera A Gomila R 《Molecules (Basel, Switzerland)》2004,9(5):278-286
A dinuclear self-assembled cationic macrocycle based on Pt(II)-N(pyridine) coordinative bonds and having competitive triflate anions, as metal counterions, is used in the construction of [2]rotaxane and [2]pseudorotaxane architectures assisted by hydrogen bonding. The kinetic lability of the Pt(II)-N(pyridine) coordinative bond controls the dynamics of the [2]rotaxane. 相似文献
66.
Cerium-doped Titanium dioxide (TiO(2)) nanoparticles are prepared by sol-gel method. Doping shifts the UV absorption edge of TiO(2) to the visible region, making it efficient for visible light photocatalysis. Incorporation of cerium decreases the effective band gap of TiO(2) and increases the Urbach energy levels. At the dopant concentrations of 0.015 and 0.025 mol the luminescence intensity increases compared to undoped TiO(2); however, the luminescence is quenched at 0.035 mol. Quenching of luminescence indicates efficient separation of charge carriers. Undoped TiO(2) is showing poor performance in the photocatalytic degradation of methyl orange under visible light. However, on cerium doping its photoactivity is increased, and is drastically enhanced at 0.035 mol of cerium. Further increase in Ce(3+) doping level to 0.045 mol results in the reduction of the photodegradation of the dye. On UV irradiation, entire samples show good photocatalytic activity up to 30 min, but their efficiency decreases when irradiation time is increased to 45 min. Irradiation for longer time results in negative charging of the TiO(2) surface with migrating electrons. The negatively charged surface repels the OH(-) ion and O(2) molecule from adsorbing on its surface thus decreasing the availability of hydroxyl and superoxide radical for dye degradation. 相似文献
67.
68.
Reported here are details on the discovery of a phosphine-catalyzed isomerization of hemiketals and subsequent reactions of the cyclic keto enol ether products. The new cycloisomerization complements a previously reported amine-catalyzed process that gave oxepinones from the same hemiketal starting materials. In the absence of functionality (R(2)) on the cyclic keto enol ether, a rapid and facile dimerization occurs, giving spiroketal products. When the enone is substituted (i.e., R(2) = Ph), the cyclic keto enol ether is sufficiently stable so that it can be isolated; it can then be further reacted in the same pot to provide the corresponding dihydropyrazoles. Both the spiroketal and dihydropyrazole products arise by a tandem reaction that begins with the novel cycloisomerization. The method allows for the rapid introduction of complexity in the products from relatively simple starting materials. It should find application in the synthesis of natural product-like molecules. 相似文献
69.
70.