The Colorimetric Detection and Determination of Palladium with Compounds Containing the p-Nitrosophenylamino Group¹

Abstract

Vol. 63 bine with the Br. Thus a smaller fraction of the 18 min. activity becomes water-soluble. Primary recombination or deactivation might, of course, occur also. Substitution into carbon bisulfide occurs slightly less often than into carbon tetrachloride.Alcohol or aniline acts to release the 18 min. bromine in inorganic form either by being attracted by Br atoms undergoing transition and reacting with them enough to prevent recombinations or substitutions or by reaction with the newly formed organic bromides while they are still activated.This tentative picture is based on the following experimental findings. (1) A portion (roughly 25%) of the 18 min. activity ejected from organic compounds in the gas and in the liquid will interchange with Br2 or react with reducing agents, but is not extracted by water. (2) Another portion is readily extracted by pure water. (3) The amount of 18 min. bromine which goes into or remains in organic form is reduced to a minimum by gaseous conditions or by adding alcohol or aniline to liquids. (4) Substitution into carbon bisulfide is observed and into carbon tetrachloride is confirmed. The substitution into carbon tetrachloride occurs either from bromine or alkyl bromides. (5) The products from the gas phase at 21 mm. pressure do not show preference for either negative or positive charged plates. (6) A small dependence of the amount of extraction from Br03on the presence of Brmay indicate that an intermediate form is involved there.

A Solid-State Nitrogen-15 Nuclear Magnetic Resonance Spectroscopic and Quantum Chemical Investigation of Nitrosoarene−Metal Interactions in Model Systems and in Heme Proteins

“…In previous work, the proton NMR spectrum of 1 in CF 3 COOH has been shown to consist of only one singlet for the N-methyl group. 33,36 This suggests that the oxygen is protonated; however, because of the relatively broad lines, there is still some uncertainty, 35 and in the X-ray structure, 58 the position of the proton in the hydrochloride salt was not detectable using a difference Fourier map. It was suggested, however, that on the basis of the long N-O bond length (1.374 Å), compared to 1.243 Å in unprotonated 1, together with the relatively long bond lengths in the phenyl ring (implying a quinonoid structure), protonation occurs on oxygen.…”

“…[28][29][30][31][32] The O-bonding of p-nitroso-N,N-dimethylaniline is presumably favored by the quinonoid structure 1a of 1, the enhanced basicity of the Osite favoring metal-oxygen coordination. major contribution of the polar resonance form 1a is evidenced by the large dipole moment of 6.90 D, 35 to be compared with only 3.14 D in nitrosobenzene itself. 36 Unfortunately, there is some uncertainty as to the fundamental vibrational frequency of the NO group in such complexes, with values of either 1500 or 1370 cm -1 being reported.…”

Colourimetric and fluorescent probes for the optical detection of palladium ions

“…p-Nitrosophenylamino derivatives (Fig. 2), 50 such as p-nitrosodiphenylamine 10, p-nitrosoaniline 11, p-nitrosodimethylaniline 12 and p-nitrosodiethylaniline 13, are common reagents that were developed in previous years to detect Pd 2+ . The reactions of these compounds with PdCl 2 and Pd(NO 3 ) 2 can generate a highly coloured complex Pd-[NOC 6 H 4 No] 2 C1 2 that can be used for the colourimetric determination of small amounts of Pd 2+ .…”

“…However, Pt 2+ and Hg 2+ can also quench its fluorescence. Kubo et al 83 described the synthesis and the fluorescence behaviour of a double-armed tetrathiacrown containing two naphthyl pendants (49)(50)(51). Extraction of metal ions in chloroform solutions containing 49-51 is verified by fluorescence spectroscopy.…”

Complexing between palladium(II) halides and p-NOC6H4NMe2 and p-NOC6H4NEt2

“…hydrogen transfer from the parent olefin to the The radiation induced dimerization of terminal olefins is known to proceed largely through a mechanism involving rapid condensation of an electron-deficient molecule with a neighboring olefin molecule, followed by intramolecular hydride transfer and electron recombination (1)(2)(3)(4)(5). The dimers resulting from this ionmolecule mechanism are exclusively monoolefinic.…”