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Wiley, Angewandte Chemie International Edition, 18(55), p. 5531-5535, 2016

DOI: 10.1002/anie.201600706

Wiley, Angewandte Chemie, 18(128), p. 5621-5625, 2016

DOI: 10.1002/ange.201600706

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All-Metal Antiaromaticity in Sb4-Type Lanthanocene Anions

This paper is available in a repository.
This paper is available in a repository.

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Abstract

Antiaromaticity, as introduced in 1965, usually refers to monocyclic systems with 4n π electrons. This concept was extended to all-metal molecules after the observation of Li3 Al4 (-) in the gas phase. However, the solid-phase counterparts have not been documented to date. Herein, we describe a series of all-metal antiaromatic anions, [Ln(η(4) -Sb4 )3 ](3-) (Ln=La, Y, Ho, Er, Lu), which were isolated as the K([2.2.2]crypt) salts and identified by single-crystal X-ray diffraction. Based on the results obtained from the chemical bonding analysis, multicenter indices, and the electron-counting rule, we conclude that the core [Ln(η(4) -Sb4 )3 ](3-) fragment of the crystal has three locally π-antiaromatic Sb4 fragments. This complex represents the first locally π-antiaromatic all-metal system in the solid state, which is stabilized by interactions of the three π-antiaromatic units with the central metal atom.