The Electrochemical Behavior of the Low-valent Transititon-metal Complexes. I. Nickel-2,2′-Dipyridyl Complexes.

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概要

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• The electrochemical behavior of zero-valent nickel-2,2′-dipyridyl complexes (Ni(dipy)<SUB>2</SUB>, Ni(CH<SUB>2</SUB>CHCN)<SUB>2</SUB>-(dipy), and Ni(NCCHCHCN)<SUB>2</SUB>(dipy)) was examined in a hexamethylphosphoric triamide solution by polarographic and ESR measurements. In the polarography, these complexes were first reduced at a very anodic potential (<I>E</I><SUB>1⁄2</SUB>: about −0.6–−0.8 V <I>vs.</I> Ag wire). At this reduction step, the anion radical of the complex was observed for all the complexes by means of ESR analysis. The spectra of the anion radicals and their <I>g</I>-values suggested the localization of an unpaired electron on the ligand side. The addition of 2,2′-dipyridyl to the solution increased the height of the second wave, the half-wave potential of which was also more anodic than that of free 2,2′-dipyridyl, and the anion radical of 2,2′-dipyridyl was observed at this reduction step. It was concluded that the dianion species formed at the second reduction step dissociated to give the 2,2′-dipyridyl anion radical, and that the anion radical of the complex was reproduced in the presence of excess 2,2′-dipyridyl.

• 公益社団法人 日本化学会の論文

著者

• Yamagishi Takamichi

  Department Of Applied Chemistry Graduate School Of Engineering Tokyo Metropolitan University

• Misono Akira

  Department of Industrial Chemistry, Faculty of Engineering, The University of Tokyo

• Uchida Yasuzo

  Department of Industrial Chemistry, Faculty of Engineering, The University of Tokyo

• Kageyama Hironori

  Department of Industrial Chemistry, Faculty of Engineering, The University of Tokyo

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