Lanthanide Complexes with 1,4,7-Trimethyl-1,4,7-triazacyclononane

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Abstract

The reaction of 1,4,7-trimethyl-1,4,7-triazacyclononane with samarium, gadolinium, and terbium chloride tetrahydrofuranates gives mononuclear complexes [LnCl3(Me3tacn)(THF)n] (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane; Ln = Sm (I), Gd (II), n = 1; Ln = Tb (III), n = 0). The treatment of complexes I or II with 1,2,4-triphenylcyclopentadienyl potassium affords mono(cyclopentadienyl) complexes [CpPh3LnCl2(Me3tacn)] (CpPh3 = = 1,2,4-triphenylcyclopentadienyl; Ln = Sm (IV), Gd (V)). Complexes IV and V are formed even when a twofold excess of CpPh3K is used. The molecular structure of complexes I–V was established by X-ray diffraction analysis (CCDC nos. 2299485 (I), 2299487 (II), 2299486 (III), 2305352 (IV), 2306051 (V)).

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About the authors

S. S. Degtyareva

Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences; Higher School of Economics

Email: kostya@xray.ineos.ac.ru
Russian Federation, Moscow; Moscow

D. A. Bardonov

Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences; Higher School of Economics

Email: kostya@xray.ineos.ac.ru
Russian Federation, Moscow; Moscow

K. A. Lysenko

Higher School of Economics; Lomonosov Moscow State University

Author for correspondence.
Email: kostya@xray.ineos.ac.ru
Russian Federation, Moscow; Moscow

M. E. Minyaev

Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences; Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Email: kostya@xray.ineos.ac.ru
Russian Federation, Moscow; Moscow

I. E. Nifantyev

Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences; Higher School of Economics; Lomonosov Moscow State University

Email: kostya@xray.ineos.ac.ru
Russian Federation, Moscow; Moscow; Moscow

D. M. Roitershtein

Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences; Higher School of Economics; Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Email: roiter@yandex.ru
Russian Federation, Moscow; Moscow; Moscow

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Supplementary files

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2. Scheme 1. Synthesis of complexes I and II

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3. Fig. 1. Molecular structure of complex I in the representation of atoms by ellipsoidal thermal vibrations (ρ = 50%). Hydrogen atoms and disorder of the coordinated THF molecule are not shown to simplify the figure

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4. Fig. 2. 1H NMR spectrum of complex I. The insert shows an enlarged fragment of the spectrum with the signal at 4.46 m.d.

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5. Scheme 2. Synthesis of complex III

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6. Fig. 3. Molecular structure of complex III in the representation of atoms by thermal vibration ellipsoids (ρ = 50%). Hydrogen atoms and disorder of the {TbCl3} fragment are not shown

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7. Scheme 3. Synthesis of complexes IV and V

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8. Fig. 4. Molecular structure of complex IV in the representation of atoms by thermal vibration ellipsoids (ρ = 50%). Hydrogen atoms, THF molecule and disorder of one of the phenyl substituents are not shown

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