Reliable Detection of Chemical Warfare Agents Using High Kinetic Energy Ion Mobility Spectrometry.

High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) ionize and separate ions at reduced pressures of 10-40 mbar and over a wide range of reduced electric field strengths / of up to 120 Td. Their reduced operating pressure is distinct from that of conventional drift tube ion mobility spectrometers that operate at ambient pressure for trace compound detection. High / can lead to a field-induced fragmentation pattern that provides more specific structural information about the analytes.

Detection of Chemical Warfare Agents with a Miniaturized High-Performance Drift Tube Ion Mobility Spectrometer Using High-Energetic Photons for Ionization.

A growing demand for low-cost gas sensors capable of detecting the smallest amounts of highly toxic substances in air, including chemical warfare agents (CWAs) and toxic industrial chemicals (TICs), has emerged in recent years. Ion mobility spectrometers (IMS) are particularly suitable for this application due to their high sensitivity and fast response times. In view of the preferred mobile use of such devices, miniaturized ion drift tubes are required as the core of IMS-based lightweight, low-cost, hand-held gas detectors.

Bridgehead isomer effects in bis(phosphido)-bridged diiron hexacarbonyl proton reduction electrocatalysts.

The influence of the substitution, orientation and structure of the phosphido bridges in [Fe(CO)(μ-PR)] electrocatalysts of proton reduction has been studied. The isomers e,a-[Fe(CO){μ-P(Ar)H}] (1a(Ar): Ar = Ph, 2'-methoxy-1,1'-binaphthyl (bn')), e,e-[Fe(CO){μ-P(Ar)H}] (1b(Ar): Ar = Ph, bn') were isolated from reactions of iron pentacarbonyl and the corresponding primary phosphine, syntheses that also afforded the phosphinidene-capped tri-iron clusters, [Fe(CO)(μ-CO)(μ-Pbn')] (2) and [Fe(CO)(μ-PAr)] (3(Ar), Ar = Ph, bn'). A ferrocenyl (Fc)-substituted dimer [Fe(CO){μ:μ'-1,2-(P(CHFc)CH)CH}] (4), in which the two phosphido bridges are linked by an o-xylyl group, was also prepared.

The design of second generation MOP-phosphonites: efficient chiral hydrosilylation of functionalised styrenes.

A series of enantiopure MOP-phosphonite ligands, with tailored steric profiles, have been synthesised and are proven to be very successful in high-yielding, regio- and enantioselective catalytic hydrosilylation reactions of substituted styrenes, affording important chiral secondary alcohols.

Zirconium-catalyzed intermolecular hydrophosphination using a chiral, air-stable primary phosphine.

Catalytic hydrophosphination of alkenes using a chiral, air-stable primary phosphine, (R)-[2'-methoxy(1,1'-binapthalen)-2-yl]phosphine, (R)-MeO-MOPH2, proceeds under mild conditions with a zirconium catalyst, [κ(5)-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH]Zr (1), to selectively furnish anti-Markovnikov, air-stable secondary phosphines or tertiary phosphines with slight modification of the protocol. An intermediate in the catalysis, [(N3N)Zr(R)-MeO-MOPH] (4), was structurally characterized.

Chiral MOP-phosphonite ligands: synthesis, characterisation and interconversion of η1,η6-(σ-P, π-arene) chelated rhodium(I) complexes.

The synthesis of rhodium(I) and iridium(I) complexes of chiral MOP-phosphonite ligands is reported. The full characterisation of η(1),η(6)-(σ-P, π-arene) chelated 18VE rhodium(I) complexes reveals hemilabile binding on the arene which has been quantitatively analysed.

MOP-phosphonites: a novel ligand class for asymmetric catalysis.

Chiral phosphonite ligands (S,R(b))-5a, (S,S(b))-5b, (R,R(b))-6a and (R,S(b))-6b are introduced, comprising a MOP-type backbone with a binol-based binaphthyl group bound to the phosphorus. Their reaction with [Pd(η(3)-C(4)H(7))Cl](2) affords η(3)-methallylpalladium chloride complexes 7a/b and 8a/b which have been isolated and structurally characterised. Solid-state and solution studies indicate subtle differences in their coordination behaviour, which ultimately affects their efficacy in the asymmetric hydrosilylation of styrene.

Taming functionality: easy-to-handle chiral phosphiranes.

Enantiopure chiral phosphiranes possessing a binaphthyl backbone demonstrate remarkable thermal stability, are highly resistant to air-oxidation and are effective ligands in catalytic asymmetric hydrosilylations.