Platinum(IV)-mediated nitrile-sulfimide coupling: a route to heterodiazadienes

Pt(IV)-mediated addition of the sulfimide Ph2S = NH and the mixed sulfide/sulfimides o- and p-[PhS(=NH)](PhS)-C6H4 by the S=NH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4[NH=C(R)N=SR'Ph]2] (R' = Ph, R = Me, Et, CH2Ph, Ph; R' = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2S=NH leads exclusively to trans-[PtCl4[NH=C(R)N=SPh2]2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4[NH=C(Me)N=SPh2]2] and the latter have been separated by column chromatography. Theoretical calculations at both HF/HF and MP2//HF levels for the cis and trans isomers of [PtCl4[NH=C(Me)N=SMe2]2] indicate a higher stability for the latter. Compounds trans-[PtCl4[E-NH=C(R)N=SPh2]2] (R = Me, Et) and cis-[PtCl4[E-NH=C(Me)N=SPh2][Z-NH=C(Me)N=SPh2]] have been characterized by X-ray crystallography. The complexes [PtCl4[NH=C(R)N=SPh2]2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4[NH=C(NH2)R]2] the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4[NH=C(R)N=SR'Ph]2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NH=C(R)=SR'Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-[PhS(=NH)](PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the coupling--in contrast to the Pt(IV) species--gives the chelates [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh]]. The X-ray crystal structure of [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh-o]] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum.     

Elucidating the hard/soft acid/base principle: a perspective based on half-reactions

A comprehensive analysis is presented for the acid-base double-exchange reaction as well as the associated acid-displacement and base-displacement "half-reactions" with the goal of elucidating the meaning of the hard/soft acid/base (HSAB) principle and the conditions for its validity. When electron-transfer effects are important and other effects are negligible, the HSAB principle is driven by the surpassing stability of the soft acid/soft base product. When electrostatic effects dominate the reactivity, the HSAB principle is driven by the surpassing stability of the hard acid/hard base product. Because electron-transfer effects favor soft/soft interactions, while electrostatic effects favor hard/hard interactions, acid-base exchange reactions may be used to determine whether a reagent's reactivity is dominated by electron-transfer or by electrostatic effects. Because electron-transfer and electrostatic considerations separately favor the HSAB principle whenever the electronic chemical potentials of the acids and bases involved in the reaction are similar, our analysis provides strong support for the HSAB principle. The electronic chemical potential measures the intrinsic strength of acids and bases.     

Chromium in biological materials — IAEA intercomparison results

Summary Some reasons for the relatively large confidence intervals for Cr in IAEA Reference Materials are critically evaluated. Possible sources of error in the determination of Cr are mentioned.

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Chrom in biologischen Materialien — Ergebnisse von IAEA-Ringversuchen

     

Nuclear-related analytical techniques: Literature retrieval from the INIS database

The applicability of the INIS database for literature retrieval on nuclear-related analytical techniques [e.g. neutron activation analysis (NAA), X-ray fluorescence (XRF), particle-induced X-ray emission (PIXE)] has been studied. There exist about 9700 documents on NAA and other forms of activation analysis, about 3500 documents on XRF and about 1200 documents on PIXE in the database collected from 1976 until July 1988. They cover a variety of elements and matrices in the fields of biology, geochemistry and the physical sciences. Some technical notes and comments on the practical use of this database are also included.     

Raman, infrared and XPS study of bamboo phytoliths after chemical digestion

Many phosphate containing minerals are found in the Jenolan Caves. Such minerals are formed by the reaction of bat guano and clays from the caves. Among these cave minerals is the mineral taranakite (K,NH(4))Al(3)(PO(4))(3)(OH)·9(H(2)O) which has been identified by X-ray diffraction. Jenolan Caves taranakite has been characterised by Raman spectroscopy. Raman and infrared bands are assigned to H(2)PO(4), OH and NH stretching vibrations. By using a combination of XRD and Raman spectroscopy, the existence of taranakite in the caves has been proven.     

Hemilability and regioselectivity in palladium and platinum complexes of dppm(E) [E = O, S, Se] ligands

Hemilability and nonrigidity in a series of mixed P^PE donor ligands where E = O, S, or Se have been studied in palladium and platinum complexes of the type [M{κ²-(dimethylamino)ethylnaphthyl-C,N)}(P^PE)][SbF₆] where P^PE = Ph₂PCH₂P(E)Ph₂.The role of the donor in hemilability, regioselectivity and the binding preferences of particular donors trans to the metallated carbon atom were also investigated. NMR parameters including couplings to ¹⁹⁵Pt and ⁷⁷Se were investigated for cis and trans isomers. The magnitude of ²J¹³C-⁷⁷Se couplings can readily distinguish the cis and trans isomers. A large through-space ¹³C-⁷⁷Se ³J coupling was observed in one of the amino methyl groups of the dppm(Se) complexes.     

Configuration interaction wavefunction for positronium hydride

A configuration interaction wavefunction is obtained for the pseudo-atom positronium hydride (consisting of one proton, one positron, and two electrons), using Slater orbitals centered on the proton as basis functions. A positive dissociation energy is calculated for the process PsH Ps + H. Comparison is made with previous calculations of this energy, and its actual value is predicted to be 0.009 au. The two-quantum annihilation rate also is calculated.

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Zusammenfassung Mit am Proton zentrierten Slaterfunktionen wird für das Pseudoatom Positroniumhydrid (aus einem Proton, einem Positron und zwei Elektronen) eine Wellenfunktion mit Konfigurationswechselwirkung aufgebaut. Für PsH Ps + H errechnet sich eine positive Dissoziationsenergie. Ihr Wert wird mit früheren Berechnungen verglichen und zu 0,009 at. E. vorhergesagt. Auch die Geschwindigkeit der Zweiquantenzerstrahlung wird berechnet.

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Résumé Sur base d'orbitales de Slater centrées sur le proton est obtenue une fonction d'onde, à interaction de configurations, pour le pseudo-atome d'hydride de positronium (un proton, un positron et deux électrons). Une énergie positive de dissociation se calcule pour PsH Ps + H. On compare aux calculs précédents et prédit sa valeur à 0.009 unités atomiques. La vitesse de décomposition en deux quanta est aussi calculée.

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Supported in part by grants to Carnegie Institute of Technology from the Petroleum Research Fund of the American Chemical Society and the National Science Foundation, and based, in part, on part of the thesis submitted by OGL in partial fulfillment of the requirements for the degree of Doctor of Philosophy, Carnegie Institute of Technology, 1961.

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National Science Foundation Predoctoral Fellow, 1960–1961.     

Static charge distributions which generate exact potential curves for diatomic molecules

For a diatomic molecule, there exists a charge density which can be used to generate the exact potential energy curve for the molecule, by integration of the classical Poisson equation. This density is displayed for H⁺₂, H₂ and LiH, and it is shown to be similar in shape to the united-atom electron density.