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

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