Triphenylstibine-substituted Fischer carbene complexes of tungsten(0): synthesis, structure, DFT and electrochemistry
Autor: | Jeanet Conradie, Armand Jansen van Rensburg, Petrus H. van Rooyen, Marrigje M. Conradie, Marilé Landman |
---|---|
Rok vydání: | 2018 |
Předmět: |
010405 organic chemistry
Aryl Transition metal carbene complex chemistry.chemical_element General Chemistry Tungsten 010402 general chemistry Electrochemistry 01 natural sciences Medicinal chemistry Catalysis 0104 chemical sciences chemistry.chemical_compound chemistry Materials Chemistry Alkoxy group Triphenylstibine Density functional theory |
Zdroj: | New Journal of Chemistry. 42:7301-7313 |
ISSN: | 1369-9261 1144-0546 |
DOI: | 10.1039/c8nj01008k |
Popis: | The synthesis, solid-state structure, and electrochemical behaviour of triphenylstibine-containing Fischer carbene complexes of tungsten(0) of the type [(SbPh3)(CO)4WC(OEt)(Ar)] with Ar = 2-thienyl (1), 2-furyl (2), 2-(N-methyl)pyrrolyl (3) or 2,2′-bithienyl (4) are reported. A density functional theory study of all the possible conformations and isomers of the various moieties in these complexes show that while the 2-furyl group adopts an anti-orientation relative to the ethoxy group, the thienyl and 2-(N-methyl)pyrrolyl adopt a cis-orientation. The preferred orientation of the aryl groups was confirmed by the solid-state structures. An electrochemical study of the complexes reveals that the decreasing order of the metal-centred oxidation and the carbene–carbon reduction of the [(SbPh3)(CO)4WC(OEt)(Ar)] complexes is: Ar = C4H3S > C4H3O > C4H3NMe. The electrochemical study further reveals substitution of a CO group in [(CO)5WC(OEt)(Ar)] with SbPh3, leads to a lowering of the metal-centred oxidation and the carbene–carbon reduction potential of ca. 0.27 and 0.13 V, respectively. |
Databáze: | OpenAIRE |
Externí odkaz: |