Monovalent Thulium. Synthesis and Properties of TmI

A. A. Fagin; Фагин А. А.; S. Yu. Bukhvalova; Бухвалова С. Ю.; V. A. Kuropatov; Куропатов В. А.; M. N. Bochkarev; Бочкарев М. Н.

doi:10.31857/S0132344X22600357

Monovalent Thulium. Synthesis and Properties of TmI

Authors: Fagin A.A.¹, Bukhvalova S.Y.¹, Kuropatov V.A.¹, Bochkarev M.N.¹
Affiliations:
1. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia
Issue: Vol 49, No 5 (2023)
Pages: 303-307
Section: Articles
URL: https://ruspoj.com/0132-344X/article/view/667514
DOI: https://doi.org/10.31857/S0132344X22600357
EDN: https://elibrary.ru/PORYUS
ID: 667514

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Abstract

The reaction of thulium shavings with iodine at 680°C gave a poorly separable product mixture A, consisting of thulium metal (65%), TmI2 (14%), and TmI (21%). Monovalent thulium iodide could not be isolated in a pure state, but its presence among the products was confirmed, apart from magnetic measurements, by reactions with naphthalene and perylene, which proceed under mild conditions. The reaction of TmI with naphthalene, which takes place at –40°C, affords the trivalent thulium complex with naphthalene dianion, [TmI(C10H8)(DME)3]. The multistep reaction with perylene starts with the formation of the divalent thulium radical anion complex, [(TmI)+(C20H12)–•(DME)3], and ends in the formation of trivalent thulium complex, [(TmI)2+(C20H12)2–(DME)3]. The presence of a radical anion intermediate in the reaction mixture in an early stage was confirmed by ESR spectroscopy.

Keywords

monovalent thulium, thulium iodide, magnetic moment, reactivity, naphthalene, perylene, radical anion

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