Inductive, steric, and environmental effects in the nonaqueous electrochemistry of hexakis(aryl isocyanide)chromium complexes
The electrochemical behavior of a series of hexakis(aryl isocyanide)chromium(I) complexes has been studied by cyclic voltammetry. The inductive effects of para substituents on E/sup 0/' for the (0 reverse arrow..-->.. 1+),(1+ reverse arrow..-->.. 2+), and (2+ reverse arrow..-->.. 3+) couples have been found to give linear correlations with the Hammett sigma/sub p/ parameter. Solvent and supporting-electrolyte effects have also been investigated and are discussed in terms of donor/acceptor theory and ion-pairing effects, respectively. The introduction of bulky ortho substituents on the aryl isocyanide ring was found to dramatically influence both the E/sup 0/'/sub 3+///sub 2+/ and the substitutional lability of the Cr(CNR)/sub 6//sup 3 +/ complexes. These effects are attributed to significant weakening of the Cr/sup III/-C bonds in the ortho-substituted complexes relative to the para-substituted complexes due to steric interactions among the ortho substituents.
- Research Organization:
- Univ of Minnesota, Minneapolis
- OSTI ID:
- 6107722
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 21:9; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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