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DOI: 10.1055/s-0042-1751538
Thermally Stable Monoruthenium Acetylide Radical Species
This work was supported by JSPS KAKENHI (21K05211) and research grants from the Inamori Foundation, the Tokyo Kasei Chemical Promotion Foundation, the Toyota Physical and Chemical Research Institute, the Tokuyama Science Foundation, the Murata Science Foundation, the Iwatani Naoji Foundation, the TEPCO Memorial Foundation, and the Tanikawa Fund Promotion of Thermal Technology.
Abstract
Control of radical reactivity is regarded as an important concern in the fields of catalysis and materials sciences. Radical species generated from monoruthenium acetylide complexes are, in general, highly reactive, and therefore structural characterization of these species has remained elusive. In this paper, a spectroscopic and structural characterization of the cationic radical species of a monoruthenium diacetylide bearing a Ru tetraphosphine fragment, [trans-(Ar–SC≡C)2Ru(dppe)2]SbCl6 ([1]+SbCl6) [Ar: p-t-BuC6H4; dppe: 1,2-bis(diphenylphosphino)ethane], is presented. The formation of the radical species [1]+ is supported by the vis-NIR, IR, and ESR studies. Furthermore, the solid-state structure of [1]+ reveals a significant contribution of the cumulenic Ru=C=C=S resonance structure. Remarkably, the thermal stability of [1]+ results from the incorporation of the electron-donating (arylsulfanyl)ethynyl ligands and the highly sterically demanding dppe ligands as compared with a monoruthenium complex with less-bulky and less-electron-rich derivatives.
Key words
radicals - stable radicals - metal acetylides - ruthenium complexes - ESR - X-ray crystallographySupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0042-1751538.
- Supporting Information
Publication History
Received: 05 November 2023
Accepted after revision: 20 November 2023
Article published online:
04 January 2024
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