Azide interaction with 4f and 5f ions in aqueous solutions. I. Trivalent ions

Journal Article · Wed Aug 31 00:00:00 EDT 1983 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00160a010· OSTI ID:5398758

Musikas, C ^[1]; Cuillerdier, C; Livet, J; Forchioni, A; Chachaty, C

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1. Centre d'Etudes Nucleaires de Fontenay-aux-Roses, France

Solvent extraction and UV, Raman, and NMR spectroscopic studies were carried out on trivalent actinide and lanthanide aqueous azido complexes. Unlike trivalent d transition ions (..beta../sub 11/ approx. = 10/sup 5/) 5f and 4f aqueous azido complexes are weak (..beta../sub 11/ approx. = 2.5 for neodymium azide complexes (Nd(N/sub 3/)/sup 2 +/)), but the trivalent actinides exhibit formation constants 1 order of magnitude higher than the lanthanides. All the spectroscopic methods indicate that we are dealing with inner-sphere complexes and actinide-lanthanide differences must be attributed to higher covalent contributions in the 5f azides. /sup 15/N NMR combined with /sup 1/H NMR served to investigate the azide binding properties. With the trivalent 5f and 4f ions the binding occurs by one of the terminal nitrogen atoms. The M-N bond distance is close to 2.75 A. The lanthanide(III)-(linear azide) moieties are bent with a bond angle close to 135/sup 0/, unlike the homologous linear thiocyanate complexes. 7 figures, 4 tables.

• OSTI ID: 5398758
• Journal Information: Inorg. Chem.; (United States), Vol. 22:18
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMERICIUM COMPLEXES
NMR SPECTRA
RAMAN SPECTRA
SOLVENT EXTRACTION
STRUCTURAL CHEMICAL ANALYSIS
ULTRAVIOLET SPECTRA
AZIDO COMPOUNDS
EUROPIUM COMPLEXES
NEODYMIUM COMPLEXES
YTTERBIUM COMPLEXES
AQUEOUS SOLUTIONS
BENZENE
CHELATING AGENTS
EQUILIBRIUM
EXPERIMENTAL DATA
MIXING
ORGANIC SOLVENTS
PH VALUE
QUANTITY RATIO
TTA
WATER
ACTINIDE COMPLEXES
AROMATICS
COMPLEXES
DATA
DISPERSIONS
EXTRACTION
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
KETONES
MIXTURES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
RARE EARTH COMPLEXES
SEPARATION PROCESSES
SOLUTIONS
SOLVENTS
SPECTRA
TRANSURANIUM COMPLEXES
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400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)