Kinetics and mechanism of the oxidation of some α‐hydroxy acids by 2,2′‐bipyridinium chlorochromate

The oxidation of glycolic, lactic, malic, and a few substituted mandelic acids by 2,2′‐bipyridinium chlorochromate (BPCC) in dimethylsulphoxide leads to the formation of corresponding oxoacids. The reaction is first order each in BPCC and the hydroxy acids. The reaction is catalyzed by the hydrogen ions. The hydrogen ion dependence has the form: k_obs = a + b [H⁺]. The oxidation of α‐deuteriomandelic acid exhibited a substantial primary kinetic isotope effect (k_H/k_d = 5.29 at 303 K). Oxidation of p‐methylmandelic acid was studied in 19 different organic solvents. The solvent effect has been analyzed by using Kamlet's and Swain's multiparametric equations. A mechanism involving a hydride ion transfer via a chromate ester is proposed. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 248–254, 2002     

Microwave spectrum,centrifugal distortion constants,dipole moment and quadrupole coupling constants of pentafluoropyridine

Pentafluoropyridine has been analysed in the frequency range of 8 to 18 GHz at dry ice temperature, using a conventional 100 kHz Stark modulated microwave spectrometer. The rotational constants and centrifugal distortion constants are A = 1481.539 ± 0.003 MHz, B = 1075.348 ± 0.004 MHz and C = 623.101 ± 0.001 MHz; and d_J = ?0.39 ± 0.06 kHz, d_JK = 1.86 ± 0.27 kHz, d_K = 0.70 ± 0.1 kHz, d_EJ = (0.3 ± 0.03) × 10^?6 and d_EK = (?1.5 ± 0.2) × 10^?6. The electric dipole moment has been found to be 0.98 ± 0.08 D and the values of the quadrupole coupling constants are x_aa = 1.94 ± 0.22 MHz, x_bb = ?4.08 ± 0.06 MHz and x_cc = 2.14 ± 0.22 MHz. A simple analysis based on Townes and Dailey theory points to a considerable increase in the π-electron density and excess charge on the nitrogen site.     

Theoretical study of structure,vibrational and electronic spectra of isomers of methyl-3-methoxy-2-propenoate

A systematic quantum mechanical study of the possible conformations, their relative stabilities, vibrational and electronic spectra and thermodynamic parameters of methyl-3-methoxy-2-propenoate has been reported for the electronic ground (S₀) and first excited (S₁) states using time-dependent and time-independent Density Functional Theory (DFT) and RHF methods in extended basis sets. Detailed studies have been restricted to the E-isomer, which is found to be substantially more stable than the Z-isomer. Four possible conformers c′Cc, c′Tc, t′Cc, t′Tc, of which the first two are most stable, have been identified in the S₀ and S₁ states. Electronic excitation to S₁ state is accompanied with a reversal in the relative stability of the c′Cc and c′Tc conformers and a substantial reduction in the rotational barrier between them, as compared with the S₀ state. Optimized geometries of these conformers in the S₀ and S₁ states are being reported. Based on suitably scaled RHF/6-31G^** and DFT/6-311G^** calculations, assignments have been provided to the fundamental vibrational bands of both these conformers in terms of frequency, form and intensity of vibrations and potential energy distribution across the symmetry coordinates in the S₀ state. A complete interpretation of the electronic spectra of the conformers has been provided.     

Preparation, XRD and Raman spectroscopic studies on new compounds RE2Hf2O7 (RE=Dy, Ho, Er, Tm, Lu, Y): Pyrochlores or defect-fluorite?

A series of compositions with the general formula RE₂Hf₂O₇ (RE=Dy, Ho, Er, Tm, Y and Lu) was prepared by a standard solid-state route and characterized by powder X-ray diffraction (XRD) and Raman spectroscopy. As per theoretical modeling reported in literature, some of these materials were predicted to exist in pyrochlore lattice. However, a careful X-ray diffraction, Raman spectroscopic and synchrotron radiation-XRD study revealed that under the experimental conditions used in the present investigation, out of all the RE₂Hf₂O₇ samples only Dy₂Hf₂O₇ has got a tendency to form a pyrochlore structure. All the other (Ho, Er, Tm, Lu, Y) hafnates crystallize in a defect-fluorite structure. In order to further ascertain these inferences, a few more RE₂Hf₂O₇ samples (La, Nd, Sm) i.e., with larger RE³⁺ ions were also prepared and the results were compared.     

Stereoselective reduction of arteannuin B and its chemical transformations

Absolute stereochemistry of dihydroarteannuin B 5 obtained by the reduction of arteannuin B 3 with Ni₂B, NaBH₄ or CdCl₂-Mg-MeOH-H₂O has been established by 2D NMR and single crystal X-ray diffraction studies. Some experiments aimed at the synthesis of dihydrodeoxyarteannuin B [C-4, 5 double bond isomer of 11] are also discussed.     

Unusual iron(III) ate complexes stabilized by Li-pi interactions

Several iron(III) complexes incorporating diamidoether ligands are described. The reaction between [Li(2)[RN(SiMe(2))](2)O] and FeX(3) (X=Cl or Br; R=2,4,6-Me(3)Ph or 2,6-iPr(2)Ph) form unusual ate complexes, [FeX(2)Li[RN(SiMe(2))](2)O](2) (2, X=Cl, R=2,4,6-Me(3)Ph; 3, X=Br, R=2,4,6-Me(3)Ph; 4, X=Cl, R=2,6-iPr(2)Ph) which are stabilized by Li-pi interactions. These dimeric iron(III)-diamido complexes exhibit magnetic behaviour characteristic of uncoupled high spin (S= 5/2 ) iron(III) centres. They also undergo halide metathesis resulting in reduced iron(II) species. Thus, reaction of 2 with alkyllithium reagents leads to the formation of iron(II) dimer [Fe[Me(3)PhN(SiMe(2))](2)O](2) (6). Similarly, the previously reported iron(III)-diamido complex [FeCl[tBuN(SiMe(2))](2)O](2) (1) reacts with LiPPh(2) to yield the iron(II) dimer [Fe[tBuN(SiMe(2))](2)O](2) but reaction with LiNPh(2) gives the iron(II) product [Fe(2)(NPh(2))(2)[tBuN(SiMe(2))](2)O] (5). Some redox chemistry is also observed as side reactions in the syntheses of 2-4, yielding THF adducts of FeX(2): the one-dimensional chain [FeBr(2)(THF)(2)](n) (7) and the cluster [Fe(4)Cl(8)(THF)(6)]. The X-ray crystal structures of 3, 5 and 7 are described.