Ligand scrambling reactions of cyano(thione)gold(I) complexes and determination of their equilibrium constants
01 Oct 2002-Canadian Journal of Chemistry (NRC Research Press Ottawa, Canada)-Vol. 80, Iss: 10, pp 1279-1284
TL;DR: In this article, a series of thiones in DMSO using 13 C and 15 N NMR spectroscopy were investigated and the equilibrium constants (Keq) were determined for scrambling of all the complexes by integrating the CN resonances in the 13 C NMR recorded at 298 K.
Abstract: Ligand scrambling reactions in cyano(thione)gold(I) complexes ((>C=S-Au-CN)) to form (Au(>C=S)2) + and (Au(CN)2) - species have been investigated for a series of thiones in DMSO using 13 C and 15 N NMR spectroscopy. Rapid approach to equilibrium occurred and resulted in distinct signals for the (>C=S-Au-CN) and (Au(CN)2) - com- plexes, both in 13 C and 15 N NMR. Equilibrium constants (Keq) were determined for scrambling of all the complexes by integrating the CN resonances in the 13 C NMR recorded at 298 K. The influence of various factors (initial concentra- tion, ionic strength, temperature, and solvent polarity) on the Keq value was examined for a representative complex (ImtAuCN (Imt = Imidazolidine-2-thione)).
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Book•
01 Jan 1976
TL;DR: The theory of pericyclic reactions was introduced in this article and applied to a wide range of applications in physical organic chemistry, such as addition and elimination reactions, nucleophilic substitution, and radical reactions.
Abstract: 1. The Covalent Bond. 2. Some Fundamentals of Physical Organic Chemistry. 3. Acids and Bases. 4. Aliphatic Nucleophilic Substitution. 5. Intramolecular Cationic Rearrangements. 6. Carbanions, Carbenes, and Electrophilic Aliphatic Substitution. 7. Addition and Elimination Reactions. 8. Reactions of Carbonyl Compounds. 9. Radical Reactions. 10. The Theory of Pericyclic Reactions. 11. Applications of the Pericyclic Selection Rules. 12. Photochemistry. Answer Book.
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TL;DR: The interaction of gold(III) with peptides and proteins and its immunochemical implications are discussed, including recent potential breakthroughs.
Abstract: Gold drugs are still amongst the most efficacious for the treatment of rheumatoid arthritis. Their mechanism of action, as well as the molecular basis of their side-effects, remain poorly understood. Current theories are reviewed, including recent potential breakthroughs. The interaction of gold(III) with peptides and proteins and its immunochemical implications are discussed.
121 citations
TL;DR: Les coordinats thiol peuvent deplacer partiellement le cyanure de Au(CN) 2 −, montrant que leur affinite pour Au(I) est tres elevee as discussed by the authors.
Abstract: Les coordinats thiol peuvent deplacer partiellement le cyanure de Au(CN) 2 − , montrant que leur affinite pour Au(I) est tres elevee. Preuves Raman et RMN de 13 C pour la formation de complexes RSAuCN − qui se dismutent en Au(CN) 2 et (RS) 2 Au −
66 citations
TL;DR: The ligand-scrambling reaction of R 3 PAuCN (to form (R 3 P) 2 Au + and Au(CN) 2 −) has been studied for R=Ph, Me, Et, i-Pr, and Cy (Cy=cyclo-C 6 H 11 ).
Abstract: The ligand-scrambling reaction of R 3 PAuCN (to form (R 3 P) 2 Au + and Au(CN) 2 −) has been studied for R=Ph, Me, Et, i-Pr, and Cy (Cy=cyclo-C 6 H 11 ). The reactions are conveniently studied by 31 P and 13 C NMR spectroscopy. The phenyl complex undergoes rapid ligand exchange and must be cooled to approximately 240 K to observe sharp resonances for the individual equilibrium components. All of the aliphatic complexes are in the slow exchange limit allowing observation by NMR spectroscopy at room temperature
65 citations