Equilibria and dynamics of Tl(edta)X[sup 2[minus]] complexes (X = halide, pseudohalide) studied by multinuclear NMR

Journal Article · Wed Dec 09 04:00:00 EST 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00051a022· OSTI ID:6947166

Blixt, J; Glaser, J ^[1]; Solymosi, P; Toth, I ^[2]

---

1. Royal Institute of Technology, Stockholm (Sweden)
2. Lajos Kossuth Univ., Debrecen (Hungary)

Equilibria and dynamics in aqueous solutions of mixed complexes Tl(edta)X[sup 2[minus]] containing ionic medium (1 M NaClO[sub 4]) have been studied by means of [sup 205]Tl-, [sup 15]N-, [sup 13]C-, and [sup 1]H-NMR and potentiometry. Individual [sup 205]Tl chemical shifts have been determined for all the investigated complexes (X = H[sub 2]O, OH, Cl, Br, CN, SCN). For the pseudohalide complexes the [sup 15]N- and [sup 13]C-NMR shifts as well as the spin-spin coupling constants J([sup 205]Tl-[sup 15]N) and J([sup 205]Tl-[sup 13]C) have also been determined. The coupling constant [sup 1]J([sup 205]Tl-[sup 13]C) for the complex Tl(edta)CN[sup 2[minus]] is remarkably large, 10 479 Hz, indicating a very strong thallium-carbon bond. The stability constants, K[sub x] = [Tl(edta)X[sup 2[minus]]]/([Tl(edta)[sup [minus]]][X[sup [minus]]]), determined by a combination of [sup 205]Tl- and [sup 13]C-NMR and potentiometry, for X = Cl, CN, and SCN are, respectively: log K[sub x] = 2.6 ([+-] = [sigma]), 8.72 ([+-] 0.03) and 2.70 ([+-] 0.03). In order to facilitate the discussion of reaction mechanisms, the crystal and molecular structure of the compound Na[sub 2][Tl(edta)CN]-3H[sub 2]O has been determined using single-crystal x-ray diffraction. This compound crystallizes in the monoclinic space group P2[sub 1]/c (no. 14) with a = 7.769 (2) [angstrom], b = 14.130 (6) [angstrom], c = 17.069 (5) [angstrom], [beta] = 101.44(2)[degree], and Z = 4.

• OSTI ID: 6947166
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:25; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMINO ACIDS
ANTITHYROID DRUGS
AQUEOUS SOLUTIONS
BROMIDES
BROMINE COMPOUNDS
CARBONIC ACID DERIVATIVES
CARBOXYLIC ACIDS
CHELATING AGENTS
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
COORDINATION NUMBER
CRYSTAL STRUCTURE
CYANIDES
DIFFRACTION
DISPERSIONS
DISSOCIATION
DRUGS
EDTA
HALIDES
HALOGEN COMPOUNDS
HORMONE ANTAGONISTS
HYDROGEN COMPOUNDS
HYDROXIDES
LIGANDS
MIXTURES
NMR SPECTRA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
PERCHLORATES
SCATTERING
SOLUTIONS
SPECTRA
THALLIUM BROMIDES
THALLIUM CHLORIDES
THALLIUM COMPLEXES
THALLIUM COMPOUNDS
THALLIUM HALIDES
THIOCYANATES
X-RAY DIFFRACTION