Issue 1, 2023

Rare-earth-metal trimethylsilylmethyl ate complexes

Abstract

En route to putative rare-earth-metal alkylidene complex Li[Lu(CH2SiMe3)2(CHSiMe3)], according to Schumann's original protocol, the reaction of YCl3 with LiCH2SiMe3 in a mixture of diethyl ether and n-pentane afforded a neosilyl ate complex of composition Li3Y(CH2SiMe3)6. Tetrametallic complex Li3Y(CH2SiMe3)6 shows an unprecedented structural motif in the solid state and was further characterized by heteronuclear 1H/13C/7Li/29Si/89Y, as well as VT NMR and DRIFT spectroscopies. Analysis of the thermolysis product via heteronuclear NMR spectroscopy and its reactivity towards benzophenone gave strong evidence for an alkylidene formation upon decomposition. Application of a similar protocol for the smallest rare-earth-metal scandium led to the isolation of ate complex [Li(thf)4][LiSc2(CH2SiMe3)8] as the preferred crystallized product. Here, the reaction of adduct ScCl3(thf)3 and LiCH2SiMe3 was performed in Et2O/n-hexane, in the absence of additional THF. The reaction of LaCl3(thf) with 3 equiv. of LiCH2SiMe3 in THF/Et2O at −40 °C yielded the ate complex [Li(thf)4][La(CH2SiMe3)4(thf)], which is the first of its kind.

Graphical abstract: Rare-earth-metal trimethylsilylmethyl ate complexes

Supplementary files

Article information

Article type
Paper
Submitted
27 Oct 2022
Accepted
18 Nov 2022
First published
18 Nov 2022

Dalton Trans., 2023,52, 44-51

Rare-earth-metal trimethylsilylmethyl ate complexes

A. Mortis, F. Kracht, T. Berger, J. Lebon, C. Maichle-Mössmer and R. Anwander, Dalton Trans., 2023, 52, 44 DOI: 10.1039/D2DT03491C

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