Abstract

AbstractThe synthesis of tricyanomethyl copper complexes has been achieved by anodic dissolution of a sacrificial copper metal and cathodic reduction of 1, 1, 3, 3‐tetracyanopropane in acetonitrile, in the presence of triphenylphosphane used as coligand. The electrogenerated tetracyanopropyl radical anion is not stable and undergoes a cleavage leading to the tricyanomethyl anion and acrylonitrile which is electropolymerized at the cathode. The reaction solution gives a neutral dimeric binuclear copper(I) complex, bis{(μ‐ tricyanomethanido)bis(triphenylphosphane)copper(I)} [Cu(μ‐C(CN)3)(PPh3)2]2 (1). A second product of the synthesis reacts with 1, 10‐phenanthroline to give bis{cis‐(μ‐cyano)bis(triphenylphos‐phane)bis(phenanthroline)dicopper(I)}‐tricyanomethanide‐tetrafluoroborate‐diacetonitrile [cis‐{Cu2(μ‐CN)(Phen)2(PPh3)2}]2[C(CN)3] · BF4 · 2CH3CN (2). The crystal structures of 1 and 2 were determined by X‐ray analysis.

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