Studies on Inner Complexes¹

Abstract

The suppressive effect of increasing resistance in the cell circuit on the maximum in the polarographic c. v. curve of mercurous ions, first discovered by Brdicka, has been confirmed. It has also been found that the maxima of oxygen, lead ions, nickel ions, and zinc ions, are all more or less suppressed by a large resistance in series with the cell, and it is concluded that the effect is of general occurrence.An explanation of this effect has been given, based on the fact that the e. m. f. actually applied across the cell decreases during the life of each mercury drop when a large external resistance is in series with the cell. Berkeley, California

Cyclometallation and NN bond cleavage of 2-(arylazo)phenols by osmium. Synthesis, structure and redox properties †

“…This ligand type is familiar as a bidentate N,O-donor forming six-membered chelate rings (2). 3 However, in a series of osmium complexes of type [Os(bpy) 2 -(L)] ϩ [bpy = 2,2Ј-bipyridine; L = 2-(arylazo)phenolate], we have recently observed a rather uncommon coordination mode of this ligand type with formation of a five-membered chelate ring (3). 2c The proximity of the phenyl ring, pendant from the uncoordinated azo-nitrogen, to osmium points to the possibility of formation of an Os-C bond at the ortho position (4).…”

The behavior of metal complexes in aqueous solutions

“…Color in chelate compounds seems to be due primarily to the structure of the compound and to the nature of the polarizable valence bond system, rather than to the type of metal involved. This is strikingly illustrated by the work of Smith and co-workers (31,32,33) on metal chelates of o-quinone monoxime, o-hydroxyazo dyes, o-hydroxyquinones, and 1-hydroxyanthraquinone illustrated schematically by formulas XXVII, XXXI, XXVIII, and XXIX, respectively. The absorption spectra of these compounds are quite characteristic /M/n (XXIX) Metal chelate of 1-hydroxyanthraquinone for the chelate, being quite different from those of the organic compound and of the aquo metal ion.…”

THE RELATION BETWEEN THE ABSORPTION SPECTRA AND CHEMICAL CONSTITUTION OF DYES. XVII. THE ABSORPTION SPECTRA OF THE COPPER, NICKEL, AND COBALT COMPOUNDS OF SOME SIMPLE ortho-HYDROXY AND ortho-AMINO AZO DYES1

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In earlier published papers on the chemistry of the metal compounds of simple o-hydroxy and o-amino azo dyes (1,2,3,4,5,6,7,8,9), no data on the absorption spectra of compounds of this type have been included. The present paper discusses the absorption spectra of a representative group of such compounds.

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