Reaction of tellurium(iv) with dithizone

With an excess of dithizone over tellurium, the extraction of Te(IV) from 1 M perchloric acid solutions into a carbon tetrachloride solution (o) of dithixone follows the relation

When the acidity is varied, again with a sufficiently large excess of dithissone, the following relation seems to be approached;

(μ=1.0).     

Miscibility of zinc sulfide and zinc phosphide

Solid solutions in the system zinc sulfide/zinc phosphide (Zn(2+)(x)S(2-2xP(2x)) were investigated using the cyclic cluster model within the semiempirical MSINDO method. Results of cyclic cluster calculations for binding energies of the perfect ZnS and Zn(3)P(2) are presented and compared with the experimental data. The miscibility of ZnS and Zn(3)P(2) over the whole composition range of 0 < x < 1 was investigated by calculating the Gibbs free energy of mixing Delta(M)G for different values of x. A miscibility gap was found at both ends of the composition range and compared with experimental data.     

Zur Bildung von Xylol-tricarbonylchrom (Dimethylbenchrotrenen) aus Di-n-butylether und Hexacarbonylchrom

The reaction of fluorenone ethyleneketal (9), diphenic anhydride as well as of biphenyls such as4 with Cr(CO)₆ in refluxing di-n-butylether (BE) gives dimethylbenchrotrenes [xylene-Cr(CO)₃,7] which are also formed by refluxing pureBE with Cr(CO)₆—although with much lower yields. Similarily, from di-n-pentylether and Cr(CO)₆ isobutyl- and 1-methyl-3-propyl-benchrotrene (13 and14) were obtained, whilst from di-n-propyl- and-hexylether, resp., and Cr(CO)₆ no benchrotrenes could be isolated.Tentative assumptions on the catalytic action of certain functional groups were confirmed by the reaction ofBE and Cr(CO)₆ in the presence of carbonamides, such as acetamide, urea and pyrrolidone, where 1,4-dimethylbenchrotrene (7 c) was formed with appreciable yields.Studies using dideuteratedBE showed that—at least for the reaction of9 with Cr(CO)₆ (giving a much lower yield of7 than with undeuteratedBE)—a simple bimolecular mechanism can be excluded.

     

EFFECT OF PHYTOCHROME ON THE BIOSYNTHESIS OF ACYCLIC AND CYCLIC CAROTENOIDS IN HIGHER PLANTS

Radish plants were grown in the presence of three different herbicides that interfere with the formation of the normal range of cyclic carotenoids, leading to an accumulation of acyclic biosynthetic intermediates, mainly phytoene (SAN 6706 and amitrole) and zeta-carotene (3852). Plants were then irradiated by four different light programs in order to gain more insight into the first steps of carotenoid biosynthesis and their control by light and phytochrome. In all cases, herbicide-treated and control, carotenoid biosynthesis was greatly enhanced by red light consistent with an effect of phytochrome on the early steps of the pathway. However, similar enhancement was also obtained after treatment with far-red light. Indeed with SAN 6706-treated plants synthesis of phytoene was stimulated to a much greater extent by far-red light given alone, than by red light. The involvement of phytochrome in the regulation of carotenoid biosynthesis appears not to be as simple as previously supposed.     

Ab initio calculations of the pi electron hamiltonian: singlet-triplet splittings

Some results of approximate ab initio calculations of the “correlation” contribution to the true parameters of the pi electron hamiltonian are presented for the ethylene molecule. In particular, by using sum-of-the-pairs type generalized perturbation theory, it is shown that there is a large core “correlation” contribution to singlet-triplet splittings within pi electron theories that results from the difference in the degree of ionicity of the isoconfigurational states.     

Systematik der Seltenerdmetall-Blei-Legierungen

Zusammenfassung Das systematische Verhalten (sowie dessen Fehlen) der Seltenerdmetall-Blei-Legierungen wird untersucht. Es wurden 12 verschiedene Verbindungsstöchiometrien beobachtet. Fast alle dreiwertigen Lanthanidenelemente bilden die PhasenR ₅Pb₃,R ₅Pb₄ undRPb₃. Von den anderen möglichen Stöchiometrien kommen, mit Ausnahme vonRPb₂, nur von einigen Lanthaniden Verbindungen vor. Die bekannten kristallographischen Daten werden durchbesprochen und die Existenz und Nichtexistenz einiger Phasen auf Grund kristallchemischer Theorien diskutiert. Das Schmelzverhalten derR-reichen Eutektika und der PhasenR ₅Pb₃,RPb₂ undRPb₃ wird dargestellt. Die bekannten Informationen über diese Legierungen werden auf der Basis der relativen Volumskontraktionen und des 4f-Beitrags zur Bindung überprüft und die Ergebnisse zu Voraussagen über die relativen Stabilitäten der VerbindungenR ₅Pb₃,RPb₂ undRPb₃ verwertet.

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Systematics of the rare earth-lead alloys

The systematic behavior (and also the lack of it) in the rare earth-lead alloys is examined. Twelve different compound stoichiometries have been observed. Nearly all of the trivalent lanthanide elements form theR ₅Pb₃,R ₅Pb₄, andRPb₃ phases. For the other stoichiometries, except for possiblyRPb₂, compounds exist for only a limited number of the lanthanide elements. The known crystallographic data are reviewed, and the existence and nonexistence of some of the phases are discussed on the basis of crystal chemistry theories. The melting behaviors of theR-rich eutectic and theR ₅Pb₃,RPb₂ andRPb₃ phases are presented. The known information on these alloys is examined on the basis of the relative volume contractions and the 4f contribution to the bonding, and the results are used to predict the relative stabilities of theR ₅Pb₃,RPb₂, andRPb₃ compounds.

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Mit 8 Abbildungen

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Herrn Prof. Dr.H. Nowotny gewidmet.

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Die Arbeiten wurden im Ames-Laboratorium der US-Atomenergie-kommission durchgeführt (Beitrag Nr. 2972).     

Absolutberechnung der Normalfrequenzen des Hydrogendifluoridions

Zusammenfassung Mit Hilfe eines einfachen quantenmechanischen Näherungsansatzes wird versucht, Bindungsabstände und Normalfrequenzen des Hydrogendifluoridions sowie des entsprechenden deuterierten Ions zu berechnen. Hierbei wird die Elektronenwechselwirkung der beiden Fluoridionen untereinander durch einen der Statistik entlehnten Ausdruck berücksichtigt. Die Methode liefert für die Abstände gute, für die Normalfrequenzen durchaus befriedigende Ergebnisse.

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On the basis of a quantum mechanical treatment the bond distances and the normal frequences of the hydrogen difluoride ion and its deuterated analogue are calculated. The electronic interaction of the two fluoride ions is approximated by a statistical calculation. The results are in fairly good agreement with the experimental values.

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Résumé Sur la base d'un traitement quantique simple, le calcul des distances de liaison et des fréquences normales est tenté pour l'ion de bifluorure d'hydrogène et son analogue deutéré. L'intéraction électronique des deux ions fluorures est approximée au moyen d'un calcul statistique. Les résultats sont en très bon accord avec les valeurs expérimentales.

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Der Deutschen Forschungsgemeinschaft danken wir für die Gewährung eines Stipendiums an Karl Hensen.     

Alkyl- and aryl-substituted corroles. 4. Solvent effects on the electrochemical and spectral properties of cobalt corroles

Solvent effects on the electrochemistry and spectroscopic properties of alkyl- and aryl-substituted corroles in nonaqueous media are reported. The oxidation and reduction of six compounds containing zero to seven phenyl or substituted phenyl groups on the macrocycle were studied in four different nonaqueous solvents (CH(2)Cl(2), PhCN, THF, and pyridine) containing 0.1 M tetra-n-butylammonium perchlorate. Dimers were formed upon oxidation of all corroles in CH(2)Cl(2), but this was not the case in the other three solvents, where either monomers or dimers were formed upon oxidation depending upon the solvent Gutmann donor number and the number or location of aryl substituents on the macrocycle. The half-wave potentials were analyzed as a function of the number of aryl substituents on the macrocycle as well as the concentration of added pyridine to PhCN solutions of the compound, and these data were combined with data from the spectroelectrochemistry experiments to determine the stoichiometry of the species actually in solution after the first oxidation or first reduction of each compound. The results of these experiments indicate that reduction of the bispyridine adduct (Cor)Co(III)(py)(2) proceeds via the monopyridine complex (Cor)Co(III)(py) to give in each case the unligated cobalt(II) corrole [(Cor)Co(II)](-). In contrast, pyridine remains coordinated after electrooxidation, and the final product was characterized as [(Cor)Co(III)(py)(2)](+).     

Theoretical evidence for the singlet diradical character of square planar nickel complexes containing two o-semiquinonato type ligands

Density functional theory and complete active space self-consistent field computations are applied to elucidate the singlet diradical character of square planar, diamagnetic nickel complexes that contain two bidentate ligands derived from o-catecholates, o-phenylenediamines, o-benzodithiolates, o-aminophenolates, and o-aminothiophenolates. In the density functional framework, the singlet diradical character is discussed within the broken symmetry formalism. The singlet-triplet energy gaps, the energy gained from symmetry breaking, the spin distribution in the lowest triplet state, and the form of the magnetic orbitals are applied as indicators for the singlet diradical character. Moreover, a new index for the diradical character is proposed that is based on symmetry breaking. All symmetry breaking criteria show that the complexes obtained from o-catecholates and o-benzodithiolates have the largest and the smallest singlet diradical character, respectively. The singlet diradical character should be intermediate for the complexes derived from o-phenylenediamines, o-aminophenolates, and o-aminothiophenolates. The diradical character of all complexes suggests the presence of Ni(II) central atoms. This is also indicated by the d-populations computed by means of the natural population analysis.