Isolation and structural characterization of a mainly ligand-based dimetallic radical

RIS ID

108674

Publication Details

Li, S., Wang, X., Zhang, Z., Zhao, Y. & Wang, X. (2015). Isolation and structural characterization of a mainly ligand-based dimetallic radical. Dalton Transactions: an international journal of inorganic chemistry, 44 (46), 19754-19757.

Abstract

A radical cation of ruthenium was isolated and structurally characterized. The EPR spectrum and theoretical calculations indicate that the spin density mainly resides on ligands. The X-ray structure shows that the change in metal-metal bond lengths is negligible upon one-electron oxidation. sp3 C-H bond activation was observed during the reaction of the parent molecule with the trityl cation, which possibly occurs via an oxidative EC mechanism: a thermodynamically favorable electron-transfer to give the radical cation intermediate, followed by the hydrogen atom abstraction to afford a cationic tetramethylfulvene complex with formation of a metal-carbon bond.

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Link to publisher version (DOI)

http://dx.doi.org/10.1039/c5dt03578c