Scholarlink

<p>The cyclopentadienyl anion is a <i>π</i>-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, Pn<sub>5</sub> (Pn = P, Sb) rings have been stabilized in a triple-decker sandwich structure, prepared via high-temperature reactions, and an example of a Bi<sub>5</sub><sup>−</sup> 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-Sb<sub>5</sub>)V–Cp]<sup>2−</sup> and [Cp–Nb(cyclo-Bi<sub>5</sub>)Nb–Cp]<sup>2−</sup>, which are stabilized by [K(18-crown-6)]<sup>+</sup> or [K(2.2.2-crypt)]<sup>+</sup> 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 E<sub>5</sub> rings (E = Sb, Bi). In contrast to free cyclo-E<sub>5</sub> (E = Sb, Bi) the cyclo-E<sub>5</sub> 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.</p><p></p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

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

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年3月18日

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

摘要

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, Bi). 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.