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- Title
Cyclic voltammetric studies of tris(alkylisocyanide)bis (triarylphosphine)cobalt(II) and tris(alkylisocyanide) bis(triarylphosphine)cobalt(I) complexes exhibiting synthetic interconvertability.
- Authors
Ahmad, Jamil; Bothata-Nareetsile, Florence; Becker, Clifford AL
- Abstract
Nine pairs of corresponding [CoI(CNR)3(PR'3)2]X, [CoII(CNR)3(PR'3)2]X2 complexes — where X = ClO4, BF4; CNR = CNCMe3, CNCHMe2, CNC6H11, CNCH2Ph; PR'3 = PPh3, P(C6H4Me-p)3, P(C6H4OMe-p)3 — have been studied using cyclic voltammetry in CH3CN solutions. All cycles are reversible, and E1/2 for the Co(I) complexes, initially oxidized, are within experimental error identical to E1/2 values for the corresponding Co(II) complexes, initially reduced. E1/2 values are strongly dependent on the triarylphosphine ligand, decreasing in the order PPh3 > > P(C6H4Me-p)3 > P(C6H4OMe-p)3, and weakly dependent on the alkylisocyanide ligand, decreasing in the order CNCH2Ph > CNCMe3 > CNC6H11 >= CNCHMe2. Solution ν(-Ne quivalent to C) IR patterns reveal that the [CoI(CNR)3(PR'3)2]X complexes do not have regular trigonal bipyramidal coordination, their structure being determined by the particular CNR ligand, while the [CoII(CNR)3(PR'3)2]X2 complexes, specifically in CF3CH2OH, appear to have regular trigonal bipyramidal coordination.
- Subjects
VOLTAMMETRY; ELECTROCHEMICAL analysis; COBALT; LIGANDS (Chemistry); CHEMISTRY
- Publication
Canadian Journal of Chemistry, 2003, Vol 81, Issue 9, p982
- ISSN
0008-4042
- Publication type
Article
- DOI
10.1139/v03-100