Werner, Daniel, Guo, Zhifang, Deacon, Glen B., and Junk, Peter C. (2025) Rare Earth Ion Size Effects in Structures of Rare Earth N,N′-bis(2-trifluoromethylphenyl)formamidinates. Zeitschrift Fur Anorganische Und Allgemeine Chemie, 652 (1). e202500202.

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Abstract

The complexes, [RE(CF3Form)3] (RE = Ce, 1, or Pr, 2) and [Y(CF3Form)3(thf)] 3, have been prepared by protolysis of the corresponding RE[N(SiMe3)2]3 complexes with N,N′-bis(2-trifluoromethylphenyl)formamidine (CF3FormH) in tetrahydrofuran (1–3) or by redox transmetallation/protolysis between the RE metal, bis(pentafluorophenyl)mercury (Hg(C6F5)2), and CF3FormH in tetrahydrofuran (1, 2), and are characterized by 1H NMR and 19F NMR spectroscopy. X-ray crystallography established 1 and 2 to contain 12-coordinate RE metals with three tetradentate F,N,N′,F′-CF3Form ligands, whereas 3 has an eight coordinate Y atom with two bidentate N,N′- and one tridentate N,N′,F-CF3Form ligands and coordinated thf, and with a further F atom within the sum of Y and F van der Waals radii but >0.25 Å more distant from Y. In 1 and 2, every CF3 group forms a F2C—F—RE bond, and the extensive F—RE bonding is preferred over coordination of thf.

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