WKB-type approximations for second-order differential equations in -algebras

Rigorous asymptotic approximations of the WKB (or Liouville-Green) type are obtained for a basis of solutions to in the framework of -algebras. Both cases and are included, thus generalizing the classical theory for scalar equations developed by F.W.J. Olver to matrix as well as to infinite-dimensional equations.

     

Reactions of Substituted Boryl Radicals with Nitroalkanes. EPR, Kinetic, and Product Studies

The radical-initiated reaction of amine-boranes and phosphine-boranes, LBH(3) (L = R(3)N, R(3)P) with aliphatic nitro compounds has been investigated in order to explore the possibility of reducing tertiary nitroalkanes to the corresponding hydrocarbons. In all the examined cases boroxy nitroxides, RN(O(*))OBLH(2), resulting from the addition of ligated boryl radicals, LBH(2)(*), to an oxygen atom of the nitro group were detected and characterized by EPR spectroscopy. This reaction occurs at room temperature with a rate constant of 1.5 x 10(7) M(-)(1) s(-)(1) for LBH(2)(*) = Me(3)NBH(2)(*) and RNO(2) = Me(3)CNO(2). The boroxy nitroxides from tertiary nitroalkanes decay by a fragmentation reaction occurring with cleavage of the nitrogen-oxygen bond, rather than of the carbon-nitrogen bond as would be required for the reduction to the corresponding alkane to take place. The Arrhenius parameters for this fragmentation have been determined in few cases.     

Formation of ferrocyanides-IV Th(IV), Nd(III), UO(2)(II) and Hg(II)

The stoichiometry of the reaction between ferrocyanide and thorium, neodymium, uranyl ion and mercury(II) has been investigated. The first three give single products irrespective of the order of addition of the reagents, but the last does not. If mercury(II) is added to ferrocyanide Hg(2)Fe(CN)(6) is obtained, but if ferrocyanide is added to mercury(II) various cyanide complexes of mercury are formed. The K(sp) values for the precipitates are reported.     

Thermally activated conduction in molecular junctions

We report temperature dependence measurements on the conductance of individual molecular wires. The results show for the first time in a molecular junction the theoretically predicted transition from coherent superexchange tunneling conductance to an activated hopping mechanism as temperature is increased.     

Investigations into the parallel kinetic resolution of 2-phenylpropanoyl chloride using quasi-enantiomeric oxazolidinones

The resolution of 2-phenylpropanoyl chloride using an equimolar combination of quasi-enantiomeric oxazolidinones is discussed. The levels of diastereoselectivity were found to be dependent upon the structural nature of the metallated oxazolidinone, temperature and metal counter-ion.     

Covalent Structures of Phosphorus: A Comprehensive Theoretical Study

Starting from earlier work by Baudler we introduce a chemical heuristic for the systematic deduction and classification of covalent partial structures of phosphorus in polycyclic phosphanes, phosphorus-rich polycyclic phosphides, and allotropes of phosphorus except the black forms. This approach is used to direct ab initio techniques (which also confirm the rules) in the quest for as yet unknown forms of molecular or macromolecular phosphorus. Based on calculated stabilities of systematically generated structural alternatives we rationalize the stabilities of Hittorf's phosphorus and of molecular P₄, confirm the possible existence of at least one other crystalline allotropic form of phosphorus, and provide insight into the probable structure of amorphous red phosphorus. In total, the combined approach of chemical heuristics and large scale ab initio calculations presented in this work supplies a coherent chemical understanding of covalent polyphosphorus structures.     

Asymmetric alkaloid synthesis from (S)-pyroglutamic acid. I. Synthesis of (S)-5-ethyl-2-pyrrolidinone

From (S)-pyroglutamic acid ( 1 ) the asymmetric synthesis of (S)-5-ethyl-2-pyrrolidinone ( 5 ) in 30% yield is described.     

The reactions of iminosulfur difluorides and chlorine monofluoride

The reactions of perfluoroalkyl- and perfluoroacyl-iminosulfur difluorides with chlorine monofluoride result in the preparation of perfluoroalkyldichloroamines and a new class of compounds N,N-dichloroperfluoroamides, R_fC(O)NCl₂, via the elimination of SF₄. The amides, FC(O)NCl₂ and CF₃C(O)NCl₂, in addition to 1,2-bis-(dichloroamino)tetrafluoroethane, Cl₂NCF₂CF₂NCl₂, are reported and characterized. The reactions of CIF with other sulfur(IV) imines proceed in an analogous manner to form perfluoroalkyl-dichloroamines via the elimination of the corresponding sulfur(IV) fluoride.     

Spectrophotometric, EPR and kinetic characterisation of the >N-O* radical from 1-hydroxybenzotriazole, a key reactive species in mediated enzymatic oxidations

Characterisation of the aminoxyl (>N-O*) radical BTNO, generated from 1-hydroxybenzotriazole (HBT) by the one-electron oxidant CAN (a Ce(IV) salt), confirms BTNO as the reactive intermediate in oxidations run with the laccase/HBT system.