Radium isotopes and <Superscript>222</Superscript>Rn in Austrian drinking waters

The activity concentrations of the Ra isotopes, ²²⁶Ra and ²²⁸Ra, as well as of ²²²Rn were measured in Austrian tap waters. Rn was extracted into a mineral oil cocktail not miscible with water and measured by liquid scintillation counting using pulse-shape analysis for α/β-separation. Ra isotopes were co-precipitated with BaSO₄ or concentrated by filtration through an element specific filter. EDTA solution was used to redissolve the precipitate as well as to release the Ra from the filter. After mixing with a cocktail, the EDTA solution was measured by liquid scintillation counting, too. From our results the effective ingestion doses for adults and 3 months old babies were calculated.     

Substituted cyclononatetraenes and nonafulvenes

Reaction of $\text{cis}$,$\text{cis}$,$\text{cis}$,$\text{cis}$-[9]annulene anion ($\text{1}$) with electrophiles ($\text{2a}$-$\text{d}$) leads to substituted $\text{cis}$,$\text{cis}$,$\text{cis}$,$\text{cis}$-1,3,5,7-cyclononatetraenes ($\text{3a}$-$\text{d}$) which are precursors for the preparation of 10- and 10,10′-donor-substituted nonafulvenes (e.g. $\text{7b′}$$\text{e′}$). The influence of solvent and temperature on the ¹H-nmr spectra of the nonafulvenes $\text{7b′}$-$\text{h′}$ has been investigated.     

Notes on recentU 4 theories of gravitation

Some of the proposed Lagrangians and their corresponding field equations for a gravitational theory based on a Riemann-Cartan space with metric-compatible connection (U ₄, theory) are compared and a new one is suggested. This Lagiangian, and that of P. von der Heyde and F. W. Hehl et al. are examined applying the Gordon-decomposition argument. Finally, Einstein's field equations with cosmological term are shown to be included in some sense, but the cosmological constant naturally has microphysical origin. To simplify notation, Cartan's calculus is used throughout.Work supported by Fonds zur Förderung der wissenschaftlichen Forschung in österreich, project No. 3666.Most of this work was carried out during the stay at the 6th Course of the International School of Cosmology and Gravitation at Erice, 1979.     

Instrumental neutron activation analysis of spruce needles and trees

Tree rings and needles of young spruce clones from the immission area of the Al-refinery Ranshofen (Upper Austria), which had ceased production in 1992, were investigated by INAA. Short time irradiation was performed for determining, Al, Mn, Ca and Cl, while the elements Na, K, Rb, Ba, Zn, Fe, Sc, Cr, Co, Br and in some samples also Ca were determined via middle- and long-lived radioisotopes. Irradiation and counting conditions are given. Accuracy and sensitivity are sufficient to describe the trends of the element concentrations in needles and with the exception of Cr, Sc and Br, in tree rings. Ca-concentrations derived from⁴⁹Ca (short-time irradiation) and⁴⁷Ca (long-time irradiation) are compared and show good agreement Additionally Mg was determined in some samples by ICP-AES and if possble, by INAA. The results are compared.     

Why are olefins oxidized by RuO4 under cleavage of the carbon-carbon bond whereas oxidation by OsO4 yields cis-diols?

Quantum chemical calculations using gradient-corrected (B3LYP) density functional theory have been carried out to investigate the mechanism of the oxidative cleavage of alkenes by ruthenium tetraoxide. The initial reaction of the tetraoxide with the olefin occurs via a [3+2] cycloaddition as in the case of osmium tetraoxide. The results clearly show that the bond cleavage does not take place at the primary adduct, but much later in the reaction path. After the formation of the ruthenium(VI)dioxo-2,5-dioxolane, the reaction proceeds with the addition of a second olefin to yield ruthenium(IV)-bis(2,5-dioxolane), which in turn becomes oxidized first to rutheniumoxo(VI)-bis(2,5-dioxolane) 6(Ru) and then to ruthenium(VIII)-dioxo-bis(2,5-dioxolane) 7(Ru). Only in complexes containing the metal center in the formal oxidation state +VIII are low activation barriers for C-C bond cleavage and exothermic formation of carbonyl compounds as products calculated. The lowest activation barrier, DeltaH(++) = 2.5 kcal/mol, is calculated for the C-C bond breaking reaction of 7(Ru) which is predicted as the pivotal intermediate of the oxidation reaction. The calculations of the oxidation reaction with OsO(4) show that those reactions where the oxidation state of the metal increases have larger activation barriers for M = Ru than for M = Os, while reactions which reduce the oxidation state have a lower activation barrier for ruthenium compounds. Also, reactions which increase the oxidation state of the metal are in the case of M = Os more exothermic than for M = Ru. In this work, all important points of the potential energy surface (PES) are reported, and the complete catalytic cycle for the oxidative cleavage of olefins by ruthenium tetraoxide is presented.     

Quantum chemical investigations and bonding analysis of iron complexes with mixed cyano and carbonyl ligands

The equilibrium structures and vibrational frequencies of the iron complexes [Fe(CN)(x)(CO)(y)](q) (x = 0-6 and y = 0-5) have been calculated at the BP86 level of theory. The nature of the Fe-CN and Fe-CO has been analyzed with an energy partitioning method. The calculated Fe-CO bond lengths are in good agreement with the results of X-ray structure analysis whereas the Fe-CN bonds are calculated somewhat longer than the experimental values. The theoretically predicted vibrational frequencies of the C-O stretching mode are always lower and the calculated CN(-) frequencies are higher than the observed fundamental modes. The results of the bonding analysis suggest that the Fe-CO binding interactions have approximately 55% electrostatic character and approximately 45% covalent character. There is a significant contribution of the pi orbital interaction to the Fe-CO covalent bonding which increases when the complexes become negatively charged. The strength of deltaE(pi) may even be larger than deltaE(sigma). The Fe-CN(-) bonds have much less pi character. The calculated binding energy of the Fe-CO pi-interactions correlates very well with the C-O stretching frequencies.     

Ansamycine, 5. Mitt., Chemie der Metacycloprodigiosine

In order to obtain a better partition of a prodigiosin derivative in biological media, two hydroxy groups were introduced into theansa-part of the molecule. The synthesis of the title compound is described in detail.     

2‐Iminoimidazoline — starke Stickstoffbasen als Koordinationspartner in der Anorganischen Chemie

2‐Iminoimidazolines — Strong Nitrogen Bases als Ligands in Inorganic Chemistry Due to the tendency of the 5‐membered cyclic fragment to accept a positive charge which yields an ylide type bonding situation, 2‐iminoimidazolines are strong nitrogen bases. They can serve as neutral ligands being 2+2 electron donors. Deprotonation leads to the anions which are potential 2+4 electron donors. We describe first the synthesis and characterization of the title compound 2‐imino‐1, 3‐dimethylimidazoline (ImNH, 8 ) and its anion 9 . Next we demonstrate their properties as ligands in complexes of main group elements and transition metals. In a third chapter we describe attempts to functionalize iminoimidazolines with the goal to create neutral ligands that coordinate in a semistable fashion. On this way we want to make a contribution to the chemistry of complex compounds directed towards catalysis.     

Soliton concept in general relativity

Soliton physics has made considerable progress in solving nonlinear problems. This paper is meant to relate the soliten concept to the stationary axisymmetric vacuum fields in general relativity. We present a functional transformation which, working as a nonlinear creation operator, generates gravitational fields of isolated sources. When applied to flat space-time (gravitational vacuum) this operation leads to a nonlinear superposition of an arbitrary number of Kerr particles. This superposition also includes the Tomimatsu-Sato fields. The functional transformations form an infinite-parameter group which contains the Kinnersley-Geroch group as a subgroup.This essay received the second award from the Gravity Research Foundation for the year 1980.-Ed.     

Chemo- and periselectivity in the addition of [OsO2(CH2)2] to ethylene: a theoretical study

Quantum chemical calculations by using density functional theory at the B3LYP level have been carried out to elucidate the reaction course for the addition of ethylene to [OsO2(CH2)2] (1). The calculations predict that the kinetically most favorable reaction proceeds with an activation barrier of 8.1 kcal mol(-1) via [3+2] addition across the O=Os=CH2 moiety. This reaction is -42.4 kcal mol(-1) exothermic. Alternatively, the [3+2] addition to the H2C=Os=CH2 fragment of 1 leads to the most stable addition product 4 (-72.7 kcal mol(-1)), yet this process has a higher activation barrier (13.0 kcal mol(-1)). The [3+2] addition to the O=Os=O fragment yielding 2 is kinetically (27.5 kcal mol(-1)) and thermodynamically (-7.0 kcal mol(-1)) the least favorable [3+2] reaction. The formal [2+2] addition to the Os=O and Os=CH2 double bonds proceeds by initial rearrangement of 1 to the metallaoxirane 1 a. The rearrangement 1-->1 a and the following [2+2] additions have significantly higher activation barriers (>30 kcal mol(-1)) than the [3+2] reactions. Another isomer of 1 is the dioxoosmacyclopropane 1 b, which is 56.2 kcal mol(-1) lower in energy than 1. The activation barrier for the 1-->1 b isomerization is 15.7 kcal mol(-1). The calculations predict that there are no energetically favorable addition reactions of ethylene with 1 b. The isomeric form 1 c containing a peroxo group is too high in energy to be relevant for the reaction course. The accuracy of the B3LYP results is corroborated by high level post-HF CCSD(T) calculations for a subset of species.