The stability of tetracoordinate nickel(I) complexes, of the type [Ni(CN)2P2]− (P=substituted phosphine), generated by cathodic reduction of the parent nickel(II) complexes, has been studied by cyclic voltammetry and double potential step techniques. Evidence has been obtained that nickel(I) complexes decay to the dimeric species Ni2(CN)2P4 via a first order chemical reaction the rate determining step being the release of a cyanide ion leading to the radical species [Ni(CN)P2]. The experimental trend obtained for the first order kinetic constants has been explained on the basis of the different “trans-effect” induced by a cyanide ligand in comparison with that induced by a phosphine group and taking into account the different basic character of the phosphine ligands.
Electroanalytical investigation on the stability of tetracoordinate nickel(I) complexes / Seeber, Renato; Gian Antonio, Mazzocchin; Gino, Bontempelli; Franco, Magno. - In: JOURNAL OF ELECTROANALYTICAL CHEMISTRY AND INTERFACIAL ELECTROCHEMISTRY. - ISSN 0022-0728. - STAMPA. - 92:(1978), pp. 215-220. [10.1016/S0022-0728(78)80180-6]
Electroanalytical investigation on the stability of tetracoordinate nickel(I) complexes
SEEBER, Renato;
1978
Abstract
The stability of tetracoordinate nickel(I) complexes, of the type [Ni(CN)2P2]− (P=substituted phosphine), generated by cathodic reduction of the parent nickel(II) complexes, has been studied by cyclic voltammetry and double potential step techniques. Evidence has been obtained that nickel(I) complexes decay to the dimeric species Ni2(CN)2P4 via a first order chemical reaction the rate determining step being the release of a cyanide ion leading to the radical species [Ni(CN)P2]. The experimental trend obtained for the first order kinetic constants has been explained on the basis of the different “trans-effect” induced by a cyanide ligand in comparison with that induced by a phosphine group and taking into account the different basic character of the phosphine ligands.
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