Thermally Stable Monoruthenium Acetylide Radical Species
Yuya Tanaka∗
a
Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
b
School of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
,
Atsushi Yashiro
b
School of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
,
Munetaka Akita∗
a
Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
b
School of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
› Author AffiliationsThis 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.
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.
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Paul F,
Malvolti F,
da Costa G,
Le Stang S,
Justaud F,
Argouarch G,
Bondon A,
Sinbandhit S,
Costuas K,
Toupet L,
Lapinte C.
Organometallics 2010; 29: 2491
31 CCDC 2299743 contains the supplementary crystallographic data for [1][SbCl6]. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
32
Paul F,
Toupet L,
Thépot J.-Y,
Costuas K,
Halet J.-F,
Lapinte C.
Organometallics 2005; 24: 5464
33 When employing magic blue as the oxidant, a UV-vis-NIR study yielded a spectrum similar to that obtained by using [FeCp2][BARF]. However, the ESI-MS spectrum displayed unidentified mass ion peaks.