Solution multinuclear (³¹P,¹¹¹Cd,⁷⁷Se) magnetic resonance studies of cadmium complexes of heterocyclic aromatic thiones and the structure of [tetrakis(2(1<i>H</i>)-pyridinethione)cadmium] nitrate, [Cd(C₅H₅NS)₄](NO₃)₂

The complex salts CdL 4 (O 3 SCF 3 ) 2 (L = 2(1H)-pyridinethione (Py2SH), 4(1H)-pyridinethione (Py4SH), or 2(1H)-quinolinethione (Q2SH)) have been synthesized by the stoichiometric reaction of Cd(O 3 SCF 3 ) 2 and the appropriate thione. Both ambient-temperature 13 C and reduced-temperature 111 Cd NMR of CdL 4 (O 3 SCF 3 ) 2 in solution are consistent with L being bound through sulfur. Reduced-temperature NMR ( 31 P, 77 Se, 111 Cd, as appropriate) of mixtures of CdL 4 (O 3 SCF 3 ) 2 and Cd(EPCy 3 ) 4 (O 3 SCF 3 ) 2 (E = Se, Cy = c-C 6 H 11 ) and of Cd(EPCy 3 ) 4 (O 3 SCF 3 ) 2 (E = S, Se) and L in solution provides evidence for various [CdL n (EPCy 3 ) 4- n ] 2+ . Similarly, reduced-temperature metal NMR of [CdL 4 ] 2+ and [CdL' 4 ] 2+ (L, L' = Py2SH, Py4SH, Q2SH; L not equal L') in solution shows the formation of [CdL n L' 4- n ] 2+ . Thus it has been demonstrated that at reduced temperature [CdL 4 ] 2+ is intact in solution and exchange of L is slow on the timescale of the metal chemical shift differences. From the NMR studies of Cd(EPCy 3 ) 4 (O 3 SCF 3 ) 2 (E = S, Se):L mixtures, the binding preferences are found to be L &gt; EPCy 3 in solution. Similarly, from the reduced temperature metal NMR spectra of mixtures where L and L' compete for Cd(II) in solution, the binding preferences are Py4SH &gt; Py2SH &gt; Q2SH. The structure of Cd(Py2SH) 4 (NO 3 ) 2 (4) has been determined by single crystal X-ray analysis. Colorless crystals of 4 are tetragonal, I4(1)/acd with 8 molecules per unit cell of dimensions a = 18.660(3), c = 15.215(3) Å. The structure is comprised of recognizable NO 3 - anions and [Cd(Py2SH) 4 ] 2+ cations. In the cations, which have S 4 symmetry, the ligands are S-bound. A network of NH···O hydrogen bonds links the cations and anions.Key words: aromatic heterocyclic thiones, cadmium complexes, phosphine chalcogenides, 111 Cd, 31 P, 77 Se NMR, X-ray crystallography.

Récupéré en direct depuis OpenAlex et désinversé. Les résumés ne sont pas conservés dans cette base de données : les index inversés représentent 8,6 Go des 9,3 Go de texte de la base, et le serveur dispose de 13 Go libres.