Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry
摘要:
The mononuclear complexes [(eta(5)-C5Me5)IrCl(L-1)] (1), [(eta(5)-C5Me5)RhCl(L-1)] (2), [(eta(6)-p-Pr'C6H4Me)RuCl(L-1)] (3) and [(eta(6)- C6Me6)RuCl(L-1)] (4) have been synthesised from pyrazine-2-carboxylic acid (HL1) and the corresponding complexes [{(eta(5)- C5Me5)IrCl2)(2)], [{(eta(5)-C5Me5)RhCl2)(2)], [{(eta(6)-p-Pr'C6H4Me)RuCl2}(2)], and [{(eta(6)-C6Me6)RuCl2}(2)], respectively. The related dinuclear complexes [{(eta(5)-C5Me5)IrCl)(2)(mu-L-2)] (5), [{(eta(5)-C5Me5)RhCl}(2)(mu-L-2)] (6), [{(n(6)-p-(PrC6H4Me)-C-i)RuCl}(2)(mu-L-2)] (7) and [(eta(6)-C6Me6)R-uCl} (2)(mu-L-2)] (8) have been obtained in a similar manner from pyrazine-2,5-dicarboxylic acid (H2L2). Compounds isomeric to the latter series, [{(eta(5)-C5Me5)IrCl}(2)(mu-L-3)] (9), [{(eta(5)-C5Me5)RhCl}(2)(mu-L-3)] (10), [{(p-Pr'C6H4Me)RuCl}(2)(mu-L-3)] (11) and [{(eta(6)-C6Me6)RuCl}(2)(mu-L-3 )] (12), have been prepared by using pyrazine-2,3-dicarboxylic acid (H2L3) instead of H2L2. The molecular structures of 2 and 3, determined by X-ray diffraction analysis, show the pyrazine-2-carboxylato moiety to act as an N,O-chelating ligand, while the structure analyses of 5-7, confirm that the pyrazine-2,5-dicarboxylato unit bridges two metal centres. The electrochemical behaviour of selected representatives has been studied by voltammetric techniques. (c) 2007 Elsevier B.V. All rights reserved.