In the context of this work, Cu(I) complexes have been prepared by electrochemical route in non-aqueous media by galvanostatic dissolution of a copper metal and concomitantly the reduction of nitriles at the cathode in an undivided electrochemical cell. The electrochemical mechanisms by which these compounds can be achieved were also investigated. The electrochemical behavior of 1,1,3,3-tetracyanopropane (TCP), malononitrile (MDN) and phenylacetonitrile (PhAN), used as starting materials, investigated both at a platinum and at a copper working electrodes revealed that TCP is reduced according to an ECEC mechanism while MDN and PhAN are reduced according to an EC mechanism. The electrosynthesis with TCP yielded [Cu(µ-C(CN)3)(PPh3)2]2 and [Cu2(µ-CN)(PPh3)6][BF4]. The analyses revealed that acrylonitrile was grafted and electropolymerized onto the cathode. A reaction between 1,10-phenanthroline (phen) and the electrolytic solution afforded {cis-[Cu2(µ-CN)(Phen)2(PPh3)2]}2[C(CN)3][BF4]⋅2CH3CN. The synthesis with MDN yielded {[Cu(CN)(PPh3)2]⋅CH3CN}n. A reaction between the polymer and 2,2'-bipyridine (bipy) on the one hand and phen on the other hand, afforded a mononuclear copper(I) complexes with the formulae [Cu(CN)(bipy)(PPh3)] and [Cu(CN)(phen)(PPh3)] respectively. Electrolysis with PhAN led to [Cu(BPVA)(PPh3)2] which where allowed to react with phen to yield [Cu(BPVA)(phen)(PPh3)], where BPVA stands for 1-benzyl-2-cyano-2-phenylvinylaminate. All these compounds were characterized by elemental analysis, FAB-, ESI- and EI-MS, 1H-, 13C-, 31P-NMR- and IR-spectroscopies respectively with single crystal X-ray analysis. |