Configuration and conformation of lithiated imines by DNMR studies and ab initio calculations

The N-isopropyl imine of lithioacetaldehyde, I, was found to exist as a 50 : 50 mixture of two isomers, as seen below 20°C by ¹H and ¹³C NMR. Comparison of the population ratio and spectral characteristics of the isomers of this and related lithiated imines leads to the conclusion that they are rotamers all of which possess the syn configuration. This conclusion is supported by calculations of the barriers to interconversion.     

An optimum tolerance region for multivariate regression

A tolerance region is a map from the sample space of one statistical model to the event space of a second statistical model having the same parameter. This paper derives an optimum β-expectation tolerance region for the multivariate regression model. A measure of power is proposed and evaluated.     

Preparation and properties of a soluble polymeric aquo ion of molybdenum(V)

An orange/brown ionic and polymeric Mo(V) ion (Mo to Na ratio 2.3:1), soluble in H₂O to give stable solutions at pH～6, with UV visible spectrum λ_max 318nm, ?(per Mo) 330OM^?1 cm^?1, has been prepared and partially characterised. Various properties are described, including the conversion to the well established Mo(V) aquo dimer, MO₂O₄²⁺, on adjustment of [H⁺] to 0.17–0.50 M, I=0.50 M (H/LiClO₄). First-order rate constants, k_obs(25°C), determined by conventional spectrophotometry give a good fit to the empirical rate law,     

The isolation and X-ray structure of a complex between lithium picrate and dibenzo-36-crown-12

The crystal structure of 2Li picrate.dibenzo-36-crown-12.2H₂O was determined by X-ray diffraction methods. The 2:1 (metal:ligand) complex crystalli     

Counterion-induced translational isomerism in a bistable [2]rotaxane

Translational isomerization can be induced by changing the anions associated with a bistable rotaxane in which the tetracationic cyclophane (blue box), cyclobis(paraquat-p-phenylene), encircles a dumbbell component containing bispyrrolotetrathiafulvalene (green) and a dioxynaphthalene (red) recognition sites. The rotaxane was isolated as both its hexafluorophosphate and tris(tetrachlorobenzenediolato)phosphate(v) (TRISPHAT(-)) salts. Photophysical measurements and NMR spectroscopy carried out in acetone (CD(3)COCD(3)) and acetonitrile (CD(3)CN) solutions reveal that the much larger TRISPHAT(-) anion favors predominantly the encirclement of the green site by the blue box.     

Omega-halonitriles: domino cyclizations to oxa- and carbocyclic nitriles

t-BuOK-induced deprotonation of omega-haloalkylnitriles generates remarkably stable potassiated nitriles. In situ deprotonation and alkylation of omega-chloroalkylnitriles with aldehyde electrophiles trigger sequential nucleophilic-electrophilic alkylations generating substituted tetrahydrofuranyl and tetrahydropyranyl nitriles. Redirecting the cyclization manifold with 5-iodopentanenitrile and a ketone causes a complementary electrophilic-nucleophilic cyclization to the corresponding carbonitrile. Collectively these cyclizations provide rapid assembly of five- and six-membered oxa- and carbocyclic nitriles demonstrating the utility of omega-halonitriles in domino alkylations.