Decarboxylation syntheses of transition metal organometallics,II.trans-carbonyl(polyhalogenophenyl)bis(triphenylphosphine)rhodium(I) compounds

Summary The rhodium(I) carboxylates,trans-RhO₂CR(CO)(PPh₃)₂ (R = C₆F₅, C₆Cl₅,p-HC₆F₄,m-HC₆F₄,o-HC₆F₄,p-McOC₆F₄, 4,5-H₂C₆F₃, 3,5-H₂C₆F₃, or 2,6-F₂C₆H₃, have been prepared by reaction of RhH(CO)(PPh₃)₃ with the appropriate polyhalogenobenzoic acids in ethanol and/or by reaction oftrans-RhCl(CO)(PPh₃)₂ with the appropriate thallous carboxylates in benzene. Decarboxylations with formation of polyhalogenoarylrhodium(I) compounds,trans-RhR(CO)(PPh₃)₂ (R = C₆F₅, C₆Cl₅,p-HC₆F₄,m-HC₆F₄,p-MeOC₆F₄, 4,5-H₂C₆F₃ or 3,5-H₂C₆F₃), have been achieved either by decomposition of the corresponding rhodium(I) carboxylates in pyridine or by reaction oftrans-RhCl(CO)(PPh₃)₂ and the thallous carboxylates in pyridine, but the derivatives R =o-HC₆F₄ or 2,6-F₂C₆H₃ could not be obtained by this method. The rate of decarboxylation decreased in the sequence R = C₆F₅ >p-MeOC₆F₄ >p-HC₆F₄ >m-HC₆F₄ > 4,5-H₂C₆F₃ > 3,5-H₂C₆F₃.Part 1, ref. 10.Preliminary communication, ref. 9.     

Conjugate addition of organolithium reagents to acrylanilide anions

Phenyllithium, $\text{n}$-butyllithium, and $\text{t}$-butyllithium were found to add to substituted acrylanilide anions to give the 1,4-addition products in fair to good yields.     

Non-radiative decay processes in isolated SO2 molecules excited within the first allowed absorption band (2500–3200 Å)

New and previously published SO₂ fluorescence emission data related to non-radiative decay processes are considered in light of the recent observations of Brus and McDonald. All the present data are consistent with the previous conclusion of Mettee that non-radiative processes in SO₂ singlet photochemistry are unimportant. It appears that any small inefficiency in the emission of light quanta for SO₂ excited at short wavelengths (2650 A) is largely due to the population of a second very short-lived state which is quenched effectively even at pressures down to 1 μ. The very low efficiency of quanta production which we observed at long wavelengths (3020 Å) appears to have its origin not only in the second easily quenched state, but more importantly, in the diffusional loss of the long-lived singlet which for these conditions has a 20-fold greated lifetime than was expected previously.     

Modifications in the simultaneous determination of carbon,hydrogen, and nitrogen

Summary Improved analytical procedures are presented for the simultaneous determination of carbon, hydrogen, and nitrogen in solid organic materials by the gas volumetric method. The accuracy is improved, and the method is less dependent upon the analyst's technique.

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Zusammenfassung Verbesserte Verfahren für die gleichzeitige gasvolumetrische Bestimmung von Kohlenstoff, Wasserstoff und Stickstoff in festen organischen Verbindungen werden beschrieben. Die Genauigkeit wurde verbessert, und die Ergebnisse sind weniger von der Arbeitstechnik des Analytikers abhängig.

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Résumé On présente une amélioration des procédés analytiques pour le dosage simultané du carbone, de l'hydrogène et de l'azote dans les matériaux solides organiques par la méthode volumétrique gazeuse. La précision est meilleure et la méthode dépend moins de la technique de l'analyste.

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Work was performed under the auspices of the U. S. Atomic Energy Commission.     

The determination of134Cs,137Cs,210Pb,226Ra and228Ra concentrations in nearshore marine sediments and seawater

Multi-radionuclide analyses of coastal marine sediments and seawater can be of considerable value in defining rates and mechanisms of nearshore processes. A preliminary study of¹³⁴Cs,¹³⁷Cs,²¹⁰Pb,²²⁶Ra and²²⁸Ra in the Clyde Sea Area has been performed. A summary of the marine geochemistries of these species and a detailed account of methods involved in their routine analysis are described.     

Oxidation of coordinated olefins: the reactions of Cl2 with trichloro(ehtylene)platinate(II)

The oxidation of [PtCl₃(C₂H₄)]- by Cl₂ in aqueous solution, to yield CH₂ClCH₂OH and [PtCl₄]^2-, has been shown to proceed through the following sequence of steps: [PtCl₃(C₂H₄)] Cl₂Cl [PtCl₅(CH₂CH₂Cl)]^2-$\text{H}{}_2\text{O}\text{(HCl)}$ [PtCl₅(CH₂CH₂OH)]^2- → [PtCl₄^2- + CH₂ClCH₂OHEach of the steps and intermediates in this mechanistic sequence has been identified and characterized.     

The identification of 10 and 11 substituted 7H-benzimidazo[2,1-a]benz[de]isoquinolin-7-ones through 1N NOE studies on their methyl p-toluenesulfonate salts

The spectral similarities of 10 and 11 substituted 7H-benzimidazo[2,1-a]benz[de]isoquinolin-7-ones hinder the identification of the individual isomers. Preparation of the 13-methyl p-toluenesulfonate salts of these compounds has allowed the assignment by the use of NOE techniques. Saturation of the N-methyl caused an NOE at H-12. The coupling pattern of H-12 then provides identification of the compound.