Redox-activated ligand-exchange reactions of tetrabutylammonium trans-bis(tert-butyl isocyanide)tetrahalogenoruthenate(III) complexes, [NBu4][RuX4(CNBut)2] (X = Cl or Br)

Autor:	David G. Humphrey, Joseph P. al Dulaimi, Robin J. H. Clark
Rok vydání:	2000
Předmět:	chemistry.chemical_compound Chemistry Ligand Isocyanide Pyridine General Chemistry Triphenylphosphine Isostructural Photochemistry Acetonitrile Medicinal chemistry Redox tert-Butyl isocyanide
Zdroj:	Journal of the Chemical Society, Dalton Transactions. :933-939
ISSN:	1364-5447 1470-479X
Popis:	In situ IR and UV-VIS spectroelectrochemical studies have shown that reduction of the ions trans-[RuX4(CNBut)2]− (X = Cl or Br) in the presence of acetonitrile or pyridine results in the formation of mer,trans-[RuX3(CNBut)2L]− (L = MeCN or py), which can be oxidised reversibly to mer,trans-[RuX3(CNBut)2L]. The same reaction carried out in the presence of triphenylphosphine or tert-butyl isocyanide yields the disubstituted product, trans,trans,trans-[RuX2(CNBut)2L2] (L = PPh3 or CNBut), which can be oxidised reversibly in each case to the isostructural monocation. Oxidation of trans-[RuX4(CNBut)2]− can also be achieved, but the products are dependent upon the identity of the halide. For X = Cl the oxidation is chemically reversible at low temperature forming trans-[RuCl4(CNBut)2], whilst for X = Br the oxidation is irreversible and, in the presence of acetonitrile, pyridine or tert-butyl isocyanide, results in the formation of mer,trans-[RuBr3(CNBut)2L] (L = MeCN or py) or mer-[RuBr3(CNBut)3] (L = CNBut). All of the redox products have been characterised in situ by IR and UV-VIS spectroscopy in as many oxidation states as possible.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::c5294d8798ca6d5eadee019a47d3840a https://doi.org/10.1039/a908241g Zobrazit plný text záznamu