A novel cage-annulated (bis-homocubyl) vinylidenecarbene has been generated and successfully trapped without any intermediacy of its cycloalkyne isomer. The greater kinetic and thermodynamic stability of the vinylidenecarbene vis-à-vis its cycloalkyne isomer has been predicted by DFT B3LYP/6-31G* calculations. The calculated results suggest the prospects of the cycloalkyne becoming amenable for...

Z. Naturforsch. 42b, 573-578 (1987); eingegangen am 8. Januar 1987 Phosphinetetracarbonyliron, Phosphitetetracarbonyliron, IR Spectra, P NMR Spectra, Fe Mössbauer Spectra A series of trigonal bipyramidal Fe(CO)4L complexes has been prepared and characterized by infrared, Fe Mössbauer and P NMR spectroscopy. A linear correlation, with a negative slope, between the CO stretching frequencies and t...

Predissociation spectra in the 2.6-3.3 μm region were observed for protonated chlorine nitrate and protonated nitric acid as well as some of their isotopomers (HXNO3, X ) H, D, 35Cl, 37Cl). Two protonated isomers of both ClONO2 and HNO3 were identified from the vibrational spectra. The lowest energy isomer was the ion-molecule complex NO2(HOX) formed by protonation of the XO group. The second i...

With the help of a recently suggested computational scheme [J. Chem. Phys. 2007, 127, 084101], Mössbauer isomer shifts are calculated within the context of density functional theory, for a series of iron containing compounds. The influence of the choice of a density functional and of the truncation of a basis set on the results of calculations is analyzed. It has been observed that the hybrid d...

Mössbauer spectroscopy is an indispensable spectroscopic technique and analytical tool in iron coordination chemistry. The linear correlation between the electron density at the nucleus ("contact density") and experimental isomer shifts has been used to link calculated contact densities to experimental isomer shifts. Here we have investigated relativistic methods of systematically increasing so...

The detailed mechanistic aspects of the ion–molecule reaction between NF and CO with formation of FCO and N have been investigated by using density functional theory and ab initio calculations. We have first located on the ground doublet and quartet B3LYP/6-3111G(d) (N,F,C,O) potential energy surfaces the various energy minima and transition structures involved in this process, and subsequently...