Studies on electrochemical and coordination behaviour of phosphiniminocyclotrithiazenes
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Bibliographic record
Abstract
Electrochemical (polarographic, cyclic voltammetric, and coulometric) and coordination behaviour of several symmetrically and unsymmetrically substituted phosphiniminocyclotrithiazenes have been studied. Polarograms of R 3 PN-S 3 N 3 (R = C 6 H 5 , p-ClC 6 H 4 , p-H 3 CC 6 H 4 , and (OC 4 H 8 N)), Ph 2 (OC 4 H 8 N)PN-S 3 N 3 , and Ph(OC 4 H 8 N) 2 PN-S 3 N 3 give two cathodic waves. Cyclic voltammograms of Ph 3 PN-S 3 N 3 (1) and (OC 4 H 8 N) 3 PN-S 3 N 3 (2) reveal nearly the same oxidation peak potential but different reduction potentials. Controlled potential electrolysis of 1 and 2 at +0.6 V indicates exocyclic cleavage and ring degradation. Cathodic reduction behaviour of Ph 3 PN-S 3 N 3 suggests the possibility for the formation of 1,5-(Ph 3 PN) 2 S 4 N 4 under electrochemical conditions. Reaction of nickel chloride hexahydrate with heterocycle 1 in 1:2 molar ratio in acetonitrile affords the complex, [Ni(S 2 N 2 H) 2 ] (A) (90% yield) and [Ph 3 PNH 2 ]Cl salt as products. Analogous reactions with other ligands of this type (two symmetrical (sym.) and three unsymmetrical (unsym.)) except 2 also give A, while ligand 2 reacts with anhyd NiCl 2 in an equimolar ratio to afford a dark green, square-planar complex ((OC 4 H 8 N) 3 PN-S 3 N·NiCl 2 (B)) whose ESCA results assist in providing its coordination details. The study reveals a high tendency of these heterocycles to different types of ring cleavage. Key words: phosphiniminocyclotrithiazenes, polarography and cyclic voltammetry, substituent effect, nickel complexes, ESCA.
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Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
Machine scores (provisional)
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