Analytische Trennung und photometrische Bestimmung von Palladium und Platin

Zusammenfassung Zur colorimetrischen Bestimmung von Palladium und Platin werden die beiden Metalle zunächst durch Extraktion mit 2-Chlorpyridin von Verunreinigungen abgetrennt. Sodann wird Pt mit einer schwach sauren Pufferlösung extrahiert und als SnCl₂-PtCl₄-Komplex bei 401 nm photometriert. Pd wird als Jodo-Chlorpyridin-Komplex bei 525 nm photometrisch bestimmt. Von den geprüften Fremdionen stört nur Ir^IV die Pt- und Au^III die Pd-Bestünmung.Der Autor möchte auch an dieser Stelle der großzügigen Hustinx Research Laboratoria, Maastricht für die Zuerkennung des Hustinx-Preises für die vorliegende Arbeit danken.Herzlichen Dank gebührt ebenfalls der Geschäftsleitung der Cilag-Chemie A.G., Schaffhausen, für die Erlaubnis zur Teilnahme an der Hustinx-Research-Laboratoria-Preisfrage.     

Pyrolysis-mass spectrometry correlations of crosslink density in natural rubber vulcanizates

A set of twelve natural rubber vulcanizates was analyzed by Curie-point pyrolysis-mass spectrometry (Py-MS). Multivariate analysis successfully correlated the Py-MS data with either total or polysulfidic crosslink density measurements. (Polysulfidic means two or more sulfurs.) The principal correlation observed was an increase in the ratio of monomer to dimer pyrolyzate yield with an increase in crosslink density. The feasibility of using Py-MS for total crosslink density determination has thus been demonstrated. The Py-MS data, however, did not allow us to distinguish different types of crosslinks.     

The utilization of chemical shift and spin-lattice (T1) relaxation time data for the discrimination of isomeric indenoisoxazoles

Treatment of 2-pivaloyl-1,3-indandione with hydroxylamine leads to the formation of a pair of isomeric indenoisoxazoles, the product formed dependent upon the cyclization conditions. Under acidic conditions, 8-t-butylindeno[1,2-c]isoxazol-7-one ( 5 ) is formed while under neutral or basic conditions, an oxime, 2 , is generated which may then be cyclized under acidic conditions to give 3-t-butylindeno[1,2-c]isoxazol-4-one ( 4 ). Although these isomeric indenoisoxazoles may be discriminated by chemical means, we were interested in developing an unequivocal method for distinguishing these and potentially other isomeric pairs by spectroscopic means. A ¹³C-nmr based method for the discrimination of these isomers which is based on the utilization of chemical shift arguments and spin-lattice relaxation data is thus presented.     

Amidinoethylation—a new reaction—IV : The amidinoethylation of alcohols: a facile synthesis of 3-alkoxy-N,N'-substituted-propanamidines

The amidinoethylation of alcohols takes place by the addition of sodium alkoxides 2 (R¹ = Me, Et) to the CC double bond of a variety of N,N'-substituted-propenamidines 1 (Method A). This illustrates the activation of the CC double bond by the conjugated amidine function and provides a new class of Michael acceptors for alcohols. However, this activation is poorer than with other nucleophiles or Michael acceptors. The amidinoethylation makes available 3-alkoxy-N,N'-substituted-amidines not easily accessible by other classical methods. However, it is demonstrated that the general N,N'-substituted-amidine synthesis via the nitrilium salts can also apply to nitrile compounds having an alkoxygroup present on the molecule (method B). Since the cyanoethylation of alcohols (4) is a very fast and facile reaction the method B is the preferred strategy for the synthesis of 3-alkoxy-N,N'-substituted-propanamidines 3.     

The mixed-aldehyde synthesis of difunctional tetraarylporphyrins

The synthesis is reported of nine unsymmetrical, meso-substituted porphyrins. Among the compounds prepared are the following 5-(R)-10,15,20-tri-p-tolylporphyrins; R = 2,6-dinitrophenyl, 4-hydroxy-3-ethoxy-phenyl, 4-hydroxy-3-methoxy-5-nitrophenyl, 5-hydroxy-2-nitrophenyl and 4-hydroxy-3-nitrophenyl. Other porphyrins reported include 5-(2-(1-butoxy)phenyl)-15-(2-nitrophenyl)-10-15-di-p-tolylporphyrin and the two 5-(R)-10-15,20-tripropylporphyrins in which R = 2-nitrophenyl and 2-hydroxyphenyl. The disubstituted porphyrins offer a rational route to the synthesis of difunctional “tailed-porphyrins”.     

Optically detected zero-field triplet state magnetic resonance in photosynthetic bacteria

Triplet state transitions of the photosynthetic bacteria Rhodospirillum Rubrum, Rhodopseudomonas Spheroides and Chromatium Vinosum in chemically reduced preparations have been observed by zero-field optical detection of magnetic resonance at 2 K. For each bacterial preparation two sharp, structureless, zero-field EPR transitions were observed as microwave-induced decreases in the fluorescence intensity of the frozen cellular preparations. The depopulating rate constants for the spin sublevels of the triplet states observed in R Rubrum and R Spheroides were also measured. The similarities of the triplet state frequencies, spectral features and intersystem crossing rates suggest a common structure for the reaction centers in the photosynthetic bacteria.     

Arylation with aryllead triacetates produced in situ by mercury-lead exchange

Reaction of a diarylmercury with lead tetraacetate to give an aryllead triacetate has been found to be a rapid reaction. The in situ generation of aryllead triacetates is thus an attractive alternative to the use of the purified reagents in the various electrophilic arylation reactions of these compounds.     

Equilibria in complexes of N-heterocyclic molecules,part XII. The reaction of hydroxide and alkoxide Ions with platinum(II) complexes of 5-nitro-1,10-phenanthroline and 2,2′-bipyridyl

Summary Bis-(5-nitro-1,10-phenanthroline)platinum(II) dichloride and diperchlorate have been prepared. The reaction between the parent cation and hydroxide ion has been studied using 1 FI n.m.r. spectroscopy and found to involve attack at the ligand. The bis-(2,2-bipyridyl)platinum(II) ion has been shown to be highly reactive towards methoxide ion. The dissociation of a 2,2-bipyridyl ligand is preceded by attack at the ligand.Part XI: R. D. Gillard, t.. A. P. Kane-Maguire and P. A. Williams,Transition Met. Chem., 2, 47 (1977).On leave from the University of Baghdad, Iraq.