Contrasting Reactions of Carbodiimides with Divalent Lanthanoid Species

Vithana, Vidushi P.;Guo, Zhifang;Deacon, Glen B.;Junk, Peter C.

Abstract

Reactions of lanthanoid species with carbodiimides (RN ═ C ═ NR′) show considerable variety. Thus, treatment of the divalent 2,6-di-tert-butyl-4-ethylphenolatosamarium complex, [Sm(OArEt)2(thf)3]·PhMe with N,N'-diisopropylcarbodiimide (iPrNCNiPr) resulted in the formation of the oxalamidinatosamarium(III) complex [(OArEt)₂Sm(μ-C₂N₄iPr₄)Sm(OArEt)₂]·2PhMe (1). In contrast, the use of the bulkier N,N'-dicyclohexylcarbodiimide (CyNCNCy) led to the formation of a formamidinatosamarium(III) complex [Sm(OArEt)2(CyNC(H)NCy)(thf)2]⋅2thf (2). Reactions between rare earth metals (RE = Yb, Eu) with one molar equivalent of bis(phenylethynyl)mercury (Hg(PhCC)2) and two molar equivalents of N,N'-dicyclohexylcarbodiimide (CyNCNCy) in tetrahydrofuran (thf) at room temperature yielded lanthanoid C-phenylethynylamidinate complexes, trivalent [YbIII{CyNC(C≡CPh)NCy}3]·2thf (3) and divalent [Eu{CyNC(C≡CPh)NCy}₂(thf)₂] (4). [Sm(OArEt)2(thf)3].PhMe was obtained from SmI2(thf)2 and the in situ generated potassium aryl oxide and is a five-coordinate monomer with a stereochemistry between trigonal bipyramidal and square pyramidal.

Journal

Chemistry - A European Journal

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Chemistry A European Journal

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1521-3765

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Wiley

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DOI

10.1002/chem.202500759