Synthesis of triple-decker sandwich compounds featuring a M–M bond through cyclo-Bi5 and cyclo-Sb5 rings

IF 19.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Nature chemistry Pub Date : 2025-03-18 DOI:10.1038/s41557-025-01765-4

Yu-He Xu, Xing Yang, Ya-Nan Yang, Lili Zhao, Gernot Frenking, Zhong-Ming Sun

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Abstract

The cyclopentadienyl anion is a π-aromatic five-membered ring ligand that is widely used in organometallic chemistry. By replacing the CH groups in cyclopentadiene with isoelectronic group-15 elements, an inorganic analogue can be obtained. In this line, Pn₅ (Pn = P, Sb) rings have been stabilized in a triple-decker sandwich structure, prepared via high-temperature reactions, and an example of a Bi₅⁻ ring stabilized in a cobalt-based inverse-sandwich-type complex has been reported. Here we report the synthesis and structural characterization of two complexes, [Cp–V(cyclo-Sb₅)V–Cp]²⁻ and [Cp–Nb(cyclo-Bi₅)Nb–Cp]²⁻, which are stabilized by [K(18-crown-6)]⁺ or [K(2.2.2-crypt)]⁺ cations at room temperature under mild conditions. Our bonding analysis through various quantum-chemical methods reveals that V‒V and Nb‒Nb bonds pass through the centre of the E₅ rings (E = Sb, Nb). In contrast to free cyclo-E₅ (E = Sb, Bi) the cyclo-E₅ moieties between Cp–E units do not possess any aromatic character because the M‒M (M = V, Nb) bond passes through the centre of the ring.

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来源期刊

Nature chemistry 化学-化学综合

CiteScore

29.60

自引率

1.40%

发文量

226

审稿时长

1.7 months

期刊介绍： Nature Chemistry is a monthly journal that publishes groundbreaking and significant research in all areas of chemistry. It covers traditional subjects such as analytical, inorganic, organic, and physical chemistry, as well as a wide range of other topics including catalysis, computational and theoretical chemistry, and environmental chemistry. The journal also features interdisciplinary research at the interface of chemistry with biology, materials science, nanotechnology, and physics. Manuscripts detailing such multidisciplinary work are encouraged, as long as the central theme pertains to chemistry. Aside from primary research, Nature Chemistry publishes review articles, news and views, research highlights from other journals, commentaries, book reviews, correspondence, and analysis of the broader chemical landscape. It also addresses crucial issues related to education, funding, policy, intellectual property, and the societal impact of chemistry. Nature Chemistry is dedicated to ensuring the highest standards of original research through a fair and rigorous review process. It offers authors maximum visibility for their papers, access to a broad readership, exceptional copy editing and production standards, rapid publication, and independence from academic societies and other vested interests. Overall, Nature Chemistry aims to be the authoritative voice of the global chemical community.