Silicon‐Bridged Homocyclopentadienides: Metal‐Assisted Facile Ring Expansion of Cyclopentadienide by Transient Imino(Metallophosphino)Silylenes

H Huaiyuan Zhu X Xufang Liu S Shicheng Dong (State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry) J Jun Zhu (Wuxi EliTe Solar Co., Wuxi, China.) S Shigeyoshi Inoue (TUM School of Natural Sciences, Department of Chemistry, Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, Garching bei München 85748, Germany)

Abstract

ABSTRACT In this study, we report the aromatic C─C bond cleavage of cyclopentadienide by transient imino(metallophosphino)silylenes through the reaction of silylene equivalents with CpCo(CO) 2 , enabling the transformation of cyclopentadienides into silicon‐bridged homocyclopentadienides. The presence of homoaromaticity in these species is substantiated by NICS and ACID analyses. Experimental observations, in conjunction with detailed quantum chemical calculations, support a mechanistic scenario that metal‐assisted, silylene‐mediated cyclopentadienide activation proceeds via a formally Büchner ring‐expansion pathway.

Article Details

Volume / Issue Vol. 1, Issue 1
Published July 30, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (5)

H

Huaiyuan Zhu

X

Xufang Liu

S

Shicheng Dong

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry

J

Jun Zhu

Wuxi EliTe Solar Co., Wuxi, China.

S

Shigeyoshi Inoue

TUM School of Natural Sciences, Department of Chemistry, Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, Garching bei München 85748, Germany