Structural Diversity of Heteroligand 1,2,4-Triphenylcyclopentadienyl-Bipyridine Complexes of Rare Earth Metals

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Abstract

The reaction of triphenylcyclopentadienyl potassium and bipyridine with lanthanum, praseodymium, erbium, lutetium, and scandium chloride tetrahydrofuranates results in the formation of binuclear [CpPh3Ln(Bipy)Cl(μ2-Cl)]2 (Ln = La (I), Pr (II)) and mononuclear [CpPh3Ln(Bipy)Cl2(THF)] (Ln = Er (III), Lu (IV), [CpPh3Sc(Bipy)Cl2] (V) complexes (CpPh3 = 1,2,4-triphenylcyclopentadienyl, Bipy = bipyridine). The decrease in the REE radius in the series La…Sc results in the formation of mononuclear instead of binuclear complexes and in a decrease in the coordination number of the central ion. The coplanar arrangement of two different π-systems gives rise to stacking interactions between the triphenylcyclopentadienyl ligand and bipyridine. The molecular structure of complexes I–V was established by X-ray diffraction analysis (CCDC nos. 2308609 (I), 2308608 (II), 2308610 (III), 2308611 (IV), 2308607 (V)).

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About the authors

D. A. Bardonov

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

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

K. A. Lysenko

National Research University, Higher School of Economics; Lomonosov Moscow State University

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

S. S. Degtyareva

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

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

I. E. Nifantiev

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

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

D. M. Roitershtein

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

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

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Supplementary files

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2. Scheme 1. Preparation of triphenylcyclopentadienyl-bipyridine complexes of lanthanum and praseodymium.

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3. Scheme 2. Synthesis of complexes III–V.

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4. Fig. 1. The structure of complex I in the representation of atoms by ellipsoids of thermal vibrations (p = 50%). Hydrogen atoms are not shown here and further to simplify the drawing.

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5. Fig. 2. The structure of complex IV in the representation of atoms by ellipsoids of thermal vibrations (p = 50%).

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6. Fig. 3. The structure of complex V in the representation of atoms by ellipsoids of thermal vibrations (p = 50%).

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7. Fig. 4. Centrosymmetric stacking dimers in the crystal structure of V.

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8. Fig. 5. The nature of the superposition of -systems involved in intramolecular stacking interactions.

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