Electrochemically induced Ligand Substitutions on : Rational Pathways to Osmium(II) Complexes

Article abstract of DOI:10.1039/DT9850000947

Following electroreduction of it is possible to stabilise and characterise the reactive monoanion ^-.This monoanion readily releases chloride to give a detectable five-co-ordinate intermediate which further reacts with a donor solvent or available ligands to produce (L = MeCN, dimethylformamide, dimethyl sulphoxide, PhCN, CO, N2, or C2H4), initially as the trans isomer.The latter can be converted into the cis form.When L = PMe2Ph, the 'trans isomer' formed is not trans- and should be formulated as trans- with a unique weakly bound phosphine.In non-co-ordinating media, concentrated solutions of undergo further reactions to form doubly and triply bridged binucler species such as and ⁺.This series of electroinitiated reactions of mer- has so far yielded over 20 separate complexes individually identified by both spectroscopic methods and voltammetric data.