Kinetics of the reaction of Di-μ-acetatodi-μ-oxalatodiaquodiruthenium(II,III) anion with N-(2-hydroxyethyl)-ethylenediaminetriacetatoaquotitanium(III)

Reduction of [Ru₂(CH₃COO)₂(C₂O₄)₂(H₂O)₂]^? by N-(2-hydroxyethyl)-ethylenediaminetriacetatoaquotitanium(III) [Ti(HEDTA)] involves several distinct stages. The first stage has a half-time of less than 1 ms, and is interpreted as a substitution reaction leading to a multinuclear intermediate. The second stage has a second-order rate constant of 5 x 10₃M^?1s^?1 [25°C, μ = 0.1 m (LiCF₃SO₃)]. The rate-limiting process for the second stage is electron transfer within the assembled multinuclear complex. Subsequent slower stages correspond to breakup of the multinuclear Ru(II)₂-Ti(IV) complex formed by electron transfer. The overall rate of reduction of this oxidant by Ti(HEDTA) is less than the corresponding rate for the reaction in which Ti³⁺ acts as reductant, mainly because the stability of the binuclear complex is reduced by the presence of the aminoacid ligand. The data are consistent with the conclusion that the ligand increases the rate of intramolecular ET, probably by reducing geometric change associated with oxidation of Ti(III) to Ti(IV).     

Phase transition in dilute solution of poly(γ-benzyl-L-glutamate) in dichloromethane at a low temperature

The dielectric constant of solutions of poly(γ-benzyl-L -glutamate) (PBLG) in dichloromethane shows a jump near 195°K, irrespective of frequency. Therefore, the discontinuity is not a dispersion phenomenon but a phase transition in the thermodynamic sense. The transition temperature is independent of the concentration in the range from 0.01 to 10% by weight, but it increases linearly with the logarithm of the molecular weight of PBLG. The height of the jump depends strongly on frequency, concentration, and molecular weight. The viscosity also changes abruptly at 195°K. These results suggest that the PBLG molecule forms a cluster like a liquid crystal or is in a random coil state below the transition point.     

The structure of arugomycin,a new anthracycline antibiotic part I. structural elucidation of degradation products,AG1, AG2 and AG3.

Based on ¹H- and ¹³C-NMR and mass spectral analysis and chemical degradation, the structures of degradation products of arugomycin (arugorol, AG1, AG2 and AG3) have been determined as shown in Fig. 1.     

Base-catalyzed homo-brook rearrangement of diastereomeric 7,8- epoxy-7(trimethylsilyl)-6-tridecanols

Semi-quantitative rate measurement of base-catalyzed 1,3-migration of a silyl group from carbon to oxygen (homo-Brook rearrangement) using four diastereomerically pure title compounds revealed that the aptitude for the migration depends markedly on the configurational environment around the trimethylsilyl group of the respective substrate.     

Stellatic acid: a new class of sesterterpenoid; X-ray crystal structure

The complete structure of a unique tricyclic sesterterpene, stellatic acid, was established by X-ray diffraction of its p-bromophenacyl ester.     

Titanium (III) induced transformations of N,N-disubstituted hydroxylamines to imines and secondary amines

The reaction of N,N-disubstituted hydroxylamines with anhydrous TiCl3 gives the corresponding imines, while that with aqueous TiCl3 gives secondary amines.