Synthesis of cationic lanthanoid tetraphenylborate crown ether complexes

Evans, David J.;Guo, Zhifang;Deacon, Glen B.;Junk, Peter C.

Abstract

The efficacy of Me3NHBPh4 as a protolytic agent in the generation of reactive lanthanoid cations has been further explored. Reaction of [Nd(BH4)3(thf)4] with Me3NHBPh4 in a 1:3 mole ratio, and dibenzo-18-crown-6 (DB18C6) in thf did not yield [Nd(thf)n][BPh4]3, but [Nd(BH4)2(DB18C6)][BPh4]⋅2THF (1), a complex primed for further functionalisation, was isolated. The structure has an eight coordinate Nd atom with two trans tridentate BH4− ligands. Redox transmetallation/protolysis (RTP) reactions between Yb metal, PhHgC6F5, and Me3NHBPh4 in the presence of 18-crown-6 (18C6) or DB18C6 in MeCN or in thf followed by work up with MeCN yields [Yb(CE)(MeCN)3][BPh4]2⋅nMeCN (CE = 18C6, n = 0 (2), and DB18C6 n = 3 (3)), the structures of which have nine coordinate Yb atoms. Two pairs of MeCN ligands are transoid, whereas the third pair have a small cis N[sbnd]Yb[sbnd]N angle. In the absence of a crown ether ligand, the RTP reaction in MeCN yields the known [Yb(MeCN)8] [BPh4]2.

Journal

Journal of Organometallic Chemistry

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1013

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1872-8651

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Elsevier

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DOI

10.1016/j.jorganchem.2024.123186