Electronic structure and special features of the analytical properties of N-nitroso-N-cyclohexylhydroxylamine and its chelates

Journal Article · Sun Feb 01 04:00:00 UTC 1987 · Sov. J. Coordinat. Chem.; (United States)

OSTI ID:6158899

Kolycheva, N V; Petrukhin, O M

The tautomerism of N-nitroso-N-cyclohexylhydroxylamine (HA), the electronic structure of the ligand in metal chelates (MA/sub n/, where M = Cu(II), Fe(III), La(III), Eu(III), Yb(III), Lu(III), and Ti(IV)), and the kinetics and mechanism of the decomposition of HA in various media have been studied by the methods of IR and Raman spectroscopy and spectrophotometry. The ratio of the tautomers, viz., the N-nitroso-N'-hydroxylamine (I) and N-hydroxydiimide N'-oxide (II), determines the stability of HA and its analogs, for example, cupferron (HL), with respect to oxidation accompanied by cleavage of the bond between the nitrogen atoms. A comparison of HA and HL has revealed that the lower is the electronegativity of the substitutent at the ..cap alpha.. nitrogen atom, the higher is the content of tautomer II, and the higher is the stability of the compound with respect to thermooxidative degradation. In the chelates MA/sub n/ and ML/sub n/ the electronic structure of the ligand varies as a function of the nature of M. It has been postulated that such mobility of the valence electron density of the ligand, which is stabilized in the chelates in different ways, depending on the electronic structure of the central atom, is the reason for the nonselectivity of HA and HL, which form complexes of similar stability with a large number of metals of differing nature, and is possibly characteristic of other reagents with group chelating properties.

• Research Organization: D.I. Mendeleev Moscow Chemical-Engineering Institute, USSR
• OSTI ID: 6158899
• Journal Information: Sov. J. Coordinat. Chem.; (United States), Journal Name: Sov. J. Coordinat. Chem.; (United States) Vol. 12:4; ISSN SJCCD
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTRA
AMINES
BINDING ENERGY
BOND ANGLE
BOND LENGTHS
CHELATES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
COMPLEXOMETRY
COPPER COMPLEXES
DECOMPOSITION
DIMENSIONS
DISTANCE
ELECTRONEGATIVITY
ELECTRONIC STRUCTURE
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
EUROPIUM COMPLEXES
FERMIONS
HYDROXYLAMINE
INFRARED SPECTRA
INTERATOMIC DISTANCES
IRON COMPLEXES
ISOMERIZATION
KINETICS
LANTHANUM COMPLEXES
LATTICE VIBRATIONS
LENGTH
LEPTONS
LIGANDS
LUTETIUM COMPLEXES
NITROSO COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
PYROLYSIS
RAMAN SPECTRA
RARE EARTH COMPLEXES
REACTION KINETICS
SPECTRA
SPECTROPHOTOMETRY
THERMOCHEMICAL PROCESSES
TITANIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
VALENCE
YTTERBIUM COMPLEXES