メタロセンの形成過程を究明 二重リングスリップ中間体の構造を初めて詳細解析――刺激応答性材料設計に新たな可能性

2026-05-21 沖縄科学技術大学院大学

© Yury Torubaev

＜関連情報＞

• https://www.oist.jp/ja/news-center/news/2026/5/21/capturing-elusive-step-molecular-sandwich-making
• https://pubs.acs.org/doi/10.1021/jacs.6c04198

二重環スリップ型ルテノセン中間体の分子構造 Molecular Structure of a Doubly Ring-Slipped Ruthenocene Intermediate

Felix Wech,Yury Torubaev,and Satoshi Takebayashi
Journal of the American Chemical Society  Published: May 21, 2026
DOI:https://doi.org/10.1021/jacs.6c04198

Abstract

We report a structural characterization of a doubly ring-slipped η¹-cyclopentadienyl ruthenocene intermediate, an analogue of putative intermediates involved in the formation and deformation of ferrocene derivatives. The thermodynamically unfavorable doubly ring-slipped intermediate was kinetically trapped using a pincer ligand, and its structure was determined using single-crystal X-ray crystallography. This intermediate quantitatively converted to a ruthenocene derivative with two η⁵-cyclopentadienyl ligands. A possible intermediate in this η¹ to η⁵ double ring-slippage was trapped by the addition of PMe₃ as an η¹, η⁵ complex. The thermodynamic preference and the kinetic barrier of the double ring-slippage were confirmed by DFT calculations, along with a possible reaction path.