Novel non-aqueous Fe(III)/Fe(II) redox couple for the catalytic oxidation of hydrogen sulfide to sulfur by air

A series of Fe(III) salts and organic solvents have been screened to develop novel non-aqueous catalysts for the conversion of H2S to sulfur. FeCl3/95% N-methylpyrrolidinone/5% H2O was found to be a most efficient non-aqueous system. The process chemistry, the proposed mechanism of catalytic oxidation of H2S, and the electrochemistry are discussed.     

Supramolecular packing of alkyl substituted Janus face all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs

This study uses X-ray crystallography, theory and Langmuir isotherm analysis to explore the conformations and molecular packing of alkyl all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs, which are prepared by direct aryl hydrogenations from alkyl- or vinyl-pentafluoroaryl benzenes. Favoured conformations retain the more polar triaxial C–F bond arrangement of the all-cis 2,3,4,5,6-pentafluorocyclohexyl ring systems with the alkyl substituent adopting an equatorial orientation, and accommodating strong supramolecular interactions between rings. Langmuir isotherm analysis on a water subphase of a long chain fatty acid and alcohol carrying terminal all-cis 2,3,4,5,6-pentafluorocyclohexyl rings do not show any indication of monolayer assembly relative to their cyclohexane analogues, instead the molecules appear to aggregate and form higher molecular assemblies prior to compression. The study indicates the power and potential of this ring system as a motif for ordering supramolecular assembly.

Theory and Langmuir isotherm analysis was used to explore the conformations and molecular packing of alkyl all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs, which are prepared by direct aryl hydrogenations from alkyl- or vinyl-pentafluoroaryl benzenes.     

Janus Face All-cis 1,2,4,5-tetrakis(trifluoromethyl)- and All-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)- Cyclohexanes

We report the synthesis of all-cis 1,2,4,5-tetrakis (trifluoromethyl)- and all-cis 1,2,3,4,5,6-hexakis (trifluoromethyl)- cyclohexanes by direct hydrogenation of precursor tetrakis- or hexakis- (trifluoromethyl)benzenes. The resultant cyclohexanes have a stereochemistry such that all the CF₃ groups are on the same face of the cyclohexyl ring. All-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)cyclohexane is the most sterically demanding of the all-cis hexakis substituted cyclohexanes prepared to date, with a barrier (ΔG) to ring inversion calculated at 27 kcal mol⁻¹. The X-ray structure of all-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)cyclohexane displays a flattened chair conformation and the electrostatic profile of this compound reveals a large diffuse negative density on the fluorine face and a focused positive density on the hydrogen face. The electropositive hydrogen face can co-ordinate chloride (K≈10³) and to a lesser extent fluoride and iodide ions. Dehydrofluorination promoted decomposition occurs with fluoride ion acting as a base.     

The X-ray Structures of (R)-2,2′-Dimethyl-1,1′-binaphthyl and (±)-2-Bromomethyl-2′-dibromomethyl-1,1′-binaphthyl

Journal of Chemical Crystallography - Molecular structures of (R)-2,2′-dimethyl-1,1′-binaphthyl [monoclinic, a?=?11.24420 (11), b?=?10.56190 (9),...     

Eigenvalue Asymptotics of the Stokes Operator for Fractal Domains

The leading asymptotic term for the function that counts theeigenvalues of the Stokes operator is determined for fairlygeneral underlying bounded domains. Moreover, the remainderis estimated in terms of the fractality of the boundary of thedomain. The results obtained resemble corresponding ones forthe Dirichlet Laplacian. 1991 Mathematics Subject Classification:35P20.     

Manipulating replication processes within a dynamic covalent framework

The reaction of an amine bearing an amidopyridine recognition site and an aldehyde bearing a carboxylic acid recognition site affords an imine that is capable of directing its own formation through a dynamic covalent replication cycle. Additionally, the amine, formed by reduction of the replicating imine, is a more efficient catalyst for the formation of the replicating imine than the imine is a catalyst for its own formation.     

Hydrogen-bond-directing effect in the ionothermal synthesis of metal coordination polymers

Four new cobalt coordination polymers, (EMIm)[Co2(TMA-H)2(44bpy)3]Br 1, (EMIm)[Co(TMA-H)(44bpy)2](44bpy)Br 2, (EMIm)[Co(TMA)(Im-H)]3 and (EMIm)2[Co(TMA)2(TED-H2)] 4, were prepared from 1-ethyl-3-methyl imidazolium bromide (EMIm-Br). All the compounds have similar two-dimensional cobalt trimesate (TMA) coordination layers but different three-dimensional supramolecular architectures that contain one of three potentially ditopic amines, 4,4'-bipyridine (44bpy), imidazole (Im-H) and triethylenediamine (TED). Two-fold interpenetration of hydrogen-bonding networks was found for 1, 2 and 4. The coordination layers of 1 and 2 are neutral while 3 and 4 have anionic molecular assemblies. The use of organic amines, that act as supramolecular bridging ligands, introduces hydrogen-bond-directing effects in the ionothermal synthesis of metal coordination polymers. Hydrogen bonding helps to align the packing between the coordination layers and control the formation of 3D supramolecular networks. In 1, hydrogen bonds between the ionic species within the channels direct the alignment of non-directional electrostatic interactions between EMIm+ and Br(-) ions, which is a rare case of a hydrogen-bond-templating effect of ionic liquids in ionothermal synthesis.