Abstract
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°′ for the (0 ↔ 1+), (1+ ↔ 2+), and (2+ ↔ 3+) couples have been found to give linear correlations with the Hammett σp 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°′3+/2+ and the substitutional lability of the Cr(CNR)63+ complexes. These effects are attributed to significant weakening of the CrIII-C bonds in the ortho-substituted complexes relative to the para-substituted complexes due to steric interactions among the ortho substituents.
Original language | English (US) |
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Pages (from-to) | 3546-3551 |
Number of pages | 6 |
Journal | Inorganic chemistry |
Volume | 21 |
Issue number | 9 |
DOIs | |
State | Published - 1982 |