Abstract
The electrochemical behaviour of di(1,2-bisdiphenylphosphinoethane)M(1) perchlorate (M = Co, Rh, Ir) has been investigated on the mercury electrode in acetonitrile under a carbon monoxide atmosphere. The reduction has been found to proceed via a two-electron step on the pentacoordinated CO adducts, thus providing evidence for the reversible addition of carbon monoxide also on the rhodium complex, and leading to anionic diphosphine carbonyl complexes. Furthermore, the results showed that d 9 cobalt complex in the presence of carbon monoxide is highly unstable and a tentative interpretation of this behaviour is suggested. Reactions of the resulting metallo anions with electrophilic reagents, such as mercuric cyanide and triphenyltin, chloride, afforded novel complexes containing metalmetal bonds.
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