Thermally Stable Monoruthenium Acetylide Radical Species

Yuya Tanaka; Atsushi Yashiro; Munetaka Akita

doi:10.1055/s-0042-1751538

Synlett, Table of Contents

Synlett 2024; 35(11): 1306-1310
DOI: 10.1055/s-0042-1751538

cluster

Japan/Netherlands Gratama Workshop

Thermally Stable Monoruthenium Acetylide Radical Species

Yuya Tanaka∗

^aLaboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan

^bSchool of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan

,

Atsushi Yashiro

^bSchool of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan

,

Munetaka Akita∗

^aLaboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan

^bSchool of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan

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Abstract

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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 crystallography

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References

References and Notes
1 Costuas K, Rigaut S. Dalton Trans. 2011; 40: 5643
2 Low PJ. Coord. Chem. Rev. 2013; 257: 1507
3 Halet J.-F, Lapinte C. Coord. Chem. Rev. 2013; 257: 1584
4 Tanaka Y, Akita M. Coord. Chem. Rev. 2019; 388: 334
5 Mishiba K, Ono M, Tanaka Y, Akita M. Chem. Eur. J. 2016; 23: 2067
6 Tanaka Y, Akita M. J. Organomet. Chem. 2018; 878: 30
7 Tanaka Y, Ono M, Akita M. Chem. Lett. 2018; 47: 1296
8 Oyama Y, Kawano R, Tanaka Y, Akita M. Dalton Trans. 2019; 48: 7432
9 Tanaka Y, Takahashi H, Akita M. ACS Org. Inorg. Au 2022; 2: 327
10 Tanaka Y, Kawano R, Akita M. Chem. Eur. J. 2022; 28: e202201358
11 Rigaut S. Dalton Trans. 2013; 42: 15859
12 Milan DC, Vezzoli A, Planje IJ, Low PJ. Dalton Trans. 2018; 47: 14125
13 Tanaka Y, Kato Y, Tada T, Fujii S, Kiguchi M, Akita M. J. Am. Chem. Soc. 2018; 140: 10080
14 Tanaka Y, Ohmura K, Fujii S, Tada T, Kiguchi M, Akita M. Inorg. Chem. 2020; 59: 13254
15 Tanaka Y, Kato Y, Sugimoto K, Kawano R, Tada T, Fujii S, Kiguchi M, Akita M. Chem. Sci. 2021; 12: 4338
16 Ogawa S, Chattopadhyay S, Tanaka Y, Ohto T, Tada T, Tada H, Fujii S, Nishino T, Akita M. Chem. Sci. 2021; 12: 10871
17 Akita M, Tanaka Y. Coord. Chem. Rev. 2022; 461: 214501
18 Park S, Jang J, Tanaka Y, Yoon HJ. Nano Lett. 2022; 22: 9693
19 Tanaka Y, Okamoto A, Fujii S, Nishino T, Akita M. Inorg. Chim. Acta 2023; 544: 121211
20 Tanaka Y, Bae Y, Ogasawara F, Suzuki K, Kobayashi S, Kaneko S, Fujii S, Nishino T, Akita M. Adv. Mater. Interfaces 2023; 10: 2202464
21 Tanaka Y, Ishisaka T, Inagaki A, Koike T, Lapinte C, Akita M. Chem. Eur. J. 2010; 16: 4762
22 Schauer PA, Low PJ. Eur. J. Inorg. Chem. 2012; 390
23 Gückel S, Safari P, Bagher Hosseini Ghazvini SM, Hall MR, Gluyas JB. G, Kaupp M, Low PJ. Organometallics 2021; 40: 346
24 Paul F, da Costa G, Bondon A, Gauthier N, Sinbandhit S, Toupet L, Costuas K, Halet J.-F, Lapinte C. Organometallics 2007; 26: 874
25 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
26 Paul F, Ellis BG, Bruce MI, Toupet L, Roisnel T, Costuas K, Halet J.-F, Lapinte C. Organometallics 2006; 25: 649
27 Johno K, Tanaka Y, Koike T, Akita M. Dalton Trans. 2011; 40: 8089
28 Yashiro A, Tanaka Y, Tada T, Fujii S, Nishino T, Akita M. Chem. Eur. J. 2021; 27: 9666
29 Paul F, Toupet L, Roisnel T, Hamon P, Lapinte C. C. R. Chim. 2005; 8: 1174
30 Tanaka Y, Morozumi N, Ohto T, Kaneko S, Naitoh Y, Tada H, Fujii S, Nishino T, Akita M. ChemRxiv 2022; preprint DOI:
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.

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