Pal, Sushanta K and Alagesan, K and Samuelson, Ashoka G and Pebler, J (1999) Synthesis and characterization of novel charge transfer complexes formed by N,N%-bis(ferrocenylmethylidene)-p-phenylenediamine and N-(ferrocenylmethylidene)aniline. In: Journal of Organometallic Chemistry, 575 (1). pp. 108-118.
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N,N'-Bis(ferrocenylmethylidene)-p-phenylenediamine 1 and N-(ferrocenylmethylidene) aniline 2 are readily synthesized by Schiff base condensation of appropriate units. Iodine (I-2), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,4-benzoquinone (CA), tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) form charge transfer complexes with 1 and 2. IR spectroscopy suggests an increase in the amount of charge transferred from the ferrocenyl ring to the oxidant in the order, I-2 < CA < TCNQ < TCNE approximate to DDQ. EPR spectra of the oxidized binuclear complexes are indicative of localized species containing iron- and carbon-centered radicals. The Mossbauer spectrum of the iodine oxidized complex of 1 reveals the presence of both Fe(III) and Fe(II) centers. Variable temperature magnetic and Mossbauer studies show that the ratio of Fe(III)/Fe(II) centers varies as a function of temperature. The larger Fe(II)/Fe(III) ratio at lower temperatures is best explained by a retro charge transfer from the iodide to the iron(III) metal center. There is negligible solvent effect on the formation of the iodine oxidized charge transfer complex of 1. (C) 1999 Elsevier Science S.A. All rights reserved.
|Item Type:||Journal Article|
|Additional Information:||Copyright of this article belongs to Elsevier Science.|
|Keywords:||Ferrocene;CT complexes;Cyclic voltammetry;IR;UV–vis;EPR;Mo¨ ssbauer spectroscopy|
|Department/Centre:||Division of Chemical Sciences > Inorganic & Physical Chemistry|
|Date Deposited:||30 Jun 2011 08:30|
|Last Modified:||30 Jun 2011 08:31|
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