Issue 10, 2024

Rare-earth metal ethylene and ethyne complexes

Abstract

Guanidinate homometallic rare-earth ethyl complexes [LLn(μ2-η1:η2-Et)(Et)]2 (Ln = Y(1-Y), Lu(1-Lu)) and heterobimetallic rare-earth ethyl complexes LLn(Et)(μ2-η1:η2-Et)(μ2-η1-Et)(AlEt2) (Ln = Y(2-Y), Lu(2-Lu)) have been synthesized by the treatment of LLn(CH2C6H4NMe2-o)2 (L = (PhCH2)2NC(NC6H3iPr2-2,6)2) with different equivalents of AlEt3 in toluene at ambient temperature. Interestingly, the unprecedented rare-earth ethyne complex [LY(μ2-η1-Et)2(AlEt)]2(μ4-η1:η1:η2:η2-C2H2) (3-Y) containing a [C2H2]4− unit was afforded from 2-Y. The formation mechanism study on 3-Y was carried out by DFT calculations. Furthermore, the nature of the bonding of 3-Y was also revealed by NBO analysis. The reactions of LLn(CH2 C6H4NMe2-o)2 (Ln = Y, Lu) with AlEt3 (4 equiv.) in toluene at 50 °C produced firstly the non-Cp rare-earth ethylene complex LY(μ3-η1:η1:η2-C2H4)[(μ2-η1-Et)(AlEt2)(μ2-η1-Et)2(AlEt)] (4-Y), and the Y/Al ethyl complex LY[(μ2-η1-Et)2(AlEt2)]2 (5-Y) as an intermediate of 4-Y was isolated from the reaction of LY(CH2C6H4NMe2-o)2 with AlEt3 (4 equiv.) in toluene at −10 °C.

Graphical abstract: Rare-earth metal ethylene and ethyne complexes

Supplementary files

Article information

Article type
Edge Article
Submitted
08 Dec 2023
Accepted
26 Jan 2024
First published
31 Jan 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 3495-3501

Rare-earth metal ethylene and ethyne complexes

W. Jiang, T. Rajeshkumar, M. Guo, Y. Lin, L. Maron and L. Zhang, Chem. Sci., 2024, 15, 3495 DOI: 10.1039/D3SC06599E

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