Reactivity of monovalent thulium

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Abstract

It was found that monovalent thulium iodide TmI in the TmIx mixture reacts with hydrogen at 200°C and atmospheric pressure, forming a hydrogenation product [TmIxH], which is confirmed by the reaction with (C6F5)3GeBr, leading to the formation of (C6F5)3GeН. In the reaction with nitrogen at 450°C, a mixture is formed containing diiodide TmI2 and a product of the composition [Tm4IN], containing a Tm–N valence bond. TmI in the TmIx mixture also reacts with phenol and phenylacetylene. In the first case, a difficult-to-separate mixture of iodide phenolates TmIx(OPh)y is formed. The reaction with PhC≡CH leads to the formation of styrene, diphenylbenzene and a mixture of triphenylbenzenes. In the reaction of TmIx with СО2, trivalent thulium iodioxalate (C2O4)TmI(DМЕ).was isolated with a high yield.

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About the authors

S. Yu. Bukhvalova

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: sv-4.4.1991@iomc.ras.ru
Russian Federation, Nizhny Novgorod

A. A. Fagin

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: sv-4.4.1991@iomc.ras.ru
Russian Federation, Nizhny Novgorod

T. A. Kovylina

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: sv-4.4.1991@iomc.ras.ru
Russian Federation, Nizhny Novgorod

T. I. Kulikova

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: sv-4.4.1991@iomc.ras.ru
Russian Federation, Nizhny Novgorod

A. V. Cherkasov

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: sv-4.4.1991@iomc.ras.ru
Russian Federation, Nizhny Novgorod

M. N. Bochkarev

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: mboch@iomc.ras.ru
Russian Federation, Nizhny Novgorod

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Supplementary files

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1. JATS XML
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2. Fig. 1. Experimental diffraction pattern of a polycrystalline sample of [TmIN] (1); calculated diffraction patterns of TmH2 hydride (2), TmN nitride (3), and metallic Tm (4).

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3. Fig. 2. Photograph (a) and spectrum (b) of the glow of the reaction of Tm with I2.

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4. Fig. 3. Fragment of the experimental diffraction pattern of the polycrystalline sample [TmIN] (1); calculated diffraction patterns of the hydride TmH2 (2) and nitride TmN (3) (the intensity values ​​of all points on the diffraction patterns are increased by 15 times).

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5. Scheme 1

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6. Scheme 2

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