Isolation of an Eleven-Atom Polydentate Carbon-Chain Chelate Obtained by Cycloaddition of a Cyclic Osmium Carbyne with an Alkyne

Congqing Zhu; Jun Zhu; Xiaoxi Zhou; Qin Zhu; Yuhui Yang; Ting Bin Wen; Haiping Xia

doi:10.1002/anie.201713391

Isolation of an Eleven-Atom Polydentate Carbon-Chain Chelate Obtained by Cycloaddition of a Cyclic Osmium Carbyne with an Alkyne

Angew Chem Int Ed Engl. 2018 Mar 12;57(12):3154-3157. doi: 10.1002/anie.201713391. Epub 2018 Feb 21.

Authors

Congqing Zhu¹, Jun Zhu¹, Xiaoxi Zhou¹, Qin Zhu¹, Yuhui Yang¹, Ting Bin Wen¹, Haiping Xia¹

Affiliation

¹ State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.

PMID: 29388726
DOI: 10.1002/anie.201713391

Abstract

Carbon ligands have long played an important role in organometallic chemistry. However, previous examples of all-carbon chelating ligands are limited. Herein, we present a novel complex with an eleven-atom carbon chain as a polydentate chelating ligand. This species was formed by the [2+2+2] cycloaddition reaction of two equivalents of an alkyne with an osmapentalyne that contains the smallest carbyne bond angle (127.9°) ever observed. Density functional calculations revealed that electron-donating groups play a key role in the stabilization of this polydentate carbon-chain chelate. This process is also the first [2+2+2] cycloaddition reaction of an alkyne with a late-transition-metal carbyne complex. This study not only enriches the chemistry of polydentate carbon-chain chelates, but also deepens our understanding of the chelating ability of carbon ligands.

Keywords: C ligands; chelation; cycloaddition; metallacycles; osmium.

Publication types

Research Support, Non-U.S. Gov't