Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
The Electrochemical Behavior of the Low-valent Transition Metal Complexes. II. Iron(0)-2,2′-Bipyridine Complexes
Akira MisonoYasuzo UchidaMasanobu HidaiTakamichi YamagishiHironori Kageyama
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1973 Volume 46 Issue 9 Pages 2769-2771


The electroreduction reaction of the zero-valent iron-2,2′-bipyridine complexes (Fe(bipy)2 and Fe(bipy)3) was studied in a hexamethylphosphoric triamide solution by polarography and ESR measurements. In the polarography, Fe(bipy)2 was first reduced at a very less negative potential (E1⁄2=−0.76V vs. Hg pool) than the first wave potential of free bipyridine (−2.37 V vs. Hg pool). In the presence of excess bipyridine, Fe(bipy)2was first reduced at −1.10 V vs. Hg pool corresponding to the second reduction step of the solution of Fe(bipy)2. The visible spectra of the solution of Fe(bipy)2 in the presence of excess bipyridine was different from that of the solution of Fe(bipy)2 only. The signal with hyperfine structure attributable to the anion radical of bipyridine was observed by means of ESR analysis of the solution electrolyzed at the potential corresponding to the second reduction step. From these results, it was concluded that [Fe(bipy)(HMPT)m] was reduced at the first step, and [Fe(bipy)2(HMPT)] was reduced at the second.

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