Reactivity of cationic gold(I) carbene complexes toward oxidative addition of bromine
| Autor: | Luciano Canovese, Fabiano Visentin, Claudio Santo, Carlo Levi |
|---|---|
| Rok vydání: | 2012 |
| Předmět: |
Mechanistic study
Settore CHIM/03 - Chimica Generale e Inorganica Bromine Stereochemistry Chemistry Au(I) carbene complexes Cationic polymerization chemistry.chemical_element Medicinal chemistry Oxidative addition Br2 oxidative addition Adduct Inorganic Chemistry chemistry.chemical_compound Materials Chemistry Reactivity (chemistry) Physical and Theoretical Chemistry Carbene |
| Zdroj: | Inorganica Chimica Acta. 391:141-149 |
| ISSN: | 0020-1693 |
| DOI: | 10.1016/j.ica.2012.05.020 |
| Popis: | We have synthesized and characterized several cationic complexes of gold(I) of the type [Au(L 1 )(L 2 )] + (L 1 = NHC, L 2 = DIC; L 1 = NHC, L 2 = NAC; L 1 = NAC, L 2 = DIC; L 1 = L 2 = NAC; NHC = N-heterocyclic carbene; NAC = N-acyclic carbene, DIC = 2,6-dimethylphenylisocyanide). The complexes of type [Au(NHC)(DIC)] + react with a slight excess of Br 2 yielding the corresponding gold(III) species [Au(NHC)(DIC)Br 2 ] + . The latter decompose with a rate that is modulated by the nature of the ancillary ligands. The oxidative addition of Br 2 to complexes of the type [Au(NHC)(NAC)] + and [Au(L)(NAC)] + (L = DIC, NAC) has been also carried out and the ensuing gold(III) derivatives [Au(NHC)(NAC)Br 2 ] + and [Au(NAC) 2 Br 2 ] + are stable in solution whereas the complex [Au(NAC)(DIC)Br 2 ] + decomposes. Finally, on the basis of kinetic studies we have proposed propose a mechanism involving a fast pre-equilibrium forming an adduct containing the starting complex and Br 2 followed by a slow rearrangement of the latter to yield the final gold(III) derivatives. |
| Databáze: | OpenAIRE |
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