Cumulated double bond systems as ligands : X. N-sulfinylaniline complexes of rhodium(I) and iridium(I) of the type [MCl(PR3)2L] in which L is coordinated via the π-NS and via the sulfur atom respectively; crystal and molecular structure of [RhCl(P-i-Pr3)2(4-MeC6H4NSO)]; determination of the 1J(103Rh15N) by 15N NMR spectroscopy

Each of the compounds [MCl(Pr₃)₂(ArylNSO)] (M = Rh^I, Ir^I; R = i-Pr, Cy: Aryl = C₆H₅, 4-MeC₆H₄, 4-ClC₆H₄, 2,4,6-Me₃C₆H₂ appears to exist as two isomers both in the solid state and in solution. The molecular and single crystal structure of one of the isomers of [RhCl(P-i-Pr)₃)₂(4-Me₆H₄NSO)] shows that the N-sulfinylaniline ligand is in the cis-configuration and coordinated to the rhodium atom via the sulfur-atom. The ligand lies in a plane which includes the rhodium atom and is in agreement with the Rh-S distance of 2.10 Å. IR results of the compounds (solid and solutions), ²¹P NMR data and ¹⁵N NMR of a ¹⁵N labelled compound, which yielded a ¹⁰³Rh¹⁵N coupling constant of 15.5 Hz, show that in the second isomer the N-sulfinylaniline ligand is probably bonded to the metal atom via the π-NS bond.The ratio of the metal-π-NS bonded isomer and the metal-S bonded isomer decreases in the order Aryl = 4-ClC₆H₄ > C₆H₅ > 4-MeC₆H₄; R = i-Pr > Cy and M = Rh > Ir. The interconversion of the two isomers is intramolecular and becomes observable on the ³¹P NMR time scale at about 40° C for M = Rh.In the case of [Ir(P-i-Pr₃)₂(4-MeC₆H₄NSO)], cyclometallation of the sul- finylaniline is observed via the ortho-carbon atom, whereas cyclometallation via P-i-Pr₃ is observed when the ortho-positions are blocked by methyl groups, e.g. when L = 2,4,6-Me₃C₆H₂NSO.     

Systematic computer-aided interpretation of vibrational spectra

The diagnostic value of an interpretation system for vibrational spectra has been investigated in relation to the number of structural units the system can cope with. For five structural units the correlated wavenumber intervals are derived from three infrared and three Raman files by the CRISE program. The interpretative value of each interval in relation to the intensity threshold is discussed. For most intervals a decrease is found on increasing the number of structural units.     

The lowest triplet state of benzene: Differences in electronic structure in two crystalline modifications of a cyclohexane host

Microwave induced delayed phosphorescence (MIDP) measurements have been performed in the 00 bands of the phosphorescence spectrum of benzene dissolved in two phases of cyclohexane. From the relative radiative rates for decay of the three zero-field levels it is concluded that on the average the symmetry of the electronic structure is lower than D_2h. In the monoclinic low temperature stable phase of cyclohexane (phase II) the structure is approximately antiquinoidal, and in the metastable phase III it is approximately quinoidal.     

Synthesis of (E)- and (Z)-fluoro-olefin analogues of potent dipeptidyl peptidase IV inhibitors

(E)- and (Z)-fluoro-olefin analogues of potent dipeptidyl peptidase IV inhibitors were synthesized. A Wadsworth-Horner-Emmons reaction, followed by amide formation and reduction of the amide were used for the construction of the α-fluoro-α,β-unsaturated amine functionality.     

DNA electrophoresis in agarose gels: a simple relation describing the length dependence of mobility

Electrophoretic mobilities of DNA molecules ranging in length from 100 to 10 000 base pairs (bp) were measured in gels of eleven concentrations of agarose from 0.5 to 1.5%. Excellent fits of the dependence of mobility on DNA length were obtained with the relationship [equation: see text] showing an e(-L/gamma) crossover, where L is the length of a DNA fragment and gamma is a crossover length ranging from 8000 to 12000 bp. The other parameters in the fit are mu(s) the mobility of short DNA with unit charge in the limit as length is extrapolated to zero, and muI, the mobility of long DNA as length is extrapolated to infinity. This exponential relationship should be a useful interpolation function for determining DNA lengths over a wide range. The simplicity of this relationship may be of more fundamental significance and suggests that some common feature dominates the electrophoresis of double stranded DNA fragments in agarose gels, regardless of length.     

Tube-excited energy-dispersive X-ray fluorescence analysis. II. Energy-dispersive X-ray fluorescence analysis of air particulate material.

The use of monoenergetic exciting radiation of molybdenum obtained with a secondary target set-up, a conventional water-cooled tungsten anode x-ray tube and a Si(Li) semiconductor detector permits many trace and minor constituents from chlorine to strontium to be determined in particulate material collected on cellulose filters. The method is rapid and economical compared to other multielement techniques. The use of one or more single-element thin-film standards to calibrate for the analysis of many elements appears to be possible, but some systematic errors must be prevented. Absorption of the fluorescent radiation is remedied by a simple correction method. The precision and the accuracy of the method were critically examined by independent analysis of a number of samples with instrumental neutron activation analysis and by interlaboratory comparisons on the same samples.