Decomposition of organometallic precursor tricarbonyl(trimethylenemethane)ruthenium Ru(C4H6)(CO)3+/0 in the gas phase investigated by thermal desorption spectrometry

Ken Miyajima; Toshiaki Nagata; Fumitaka Mafuné; Tomohiro Tsugawa; Ryosuke Harada

doi:10.1039/D5CP00200A

Decomposition of organometallic precursor tricarbonyl(trimethylenemethane)ruthenium Ru(C₄H₆)(CO)₃^+/0 in the gas phase investigated by thermal desorption spectrometry†

Ken Miyajima,

*^a Toshiaki Nagata,

^b Fumitaka Mafuné,

^b Tomohiro Tsugawa^c and Ryosuke Harada^c

Author affiliations

* Corresponding authors

^a KOMEX, School of Arts and Sciences, The University of Tokyo, Komaba, Meguro, Tokyo 153-8902, Japan
E-mail: miyajima@cluster.c.u-tokyo.ac.jp

^b Department of Basic Science, School of Arts and Sciences, The University of Tokyo, Komaba, Meguro, Tokyo 153-8902, Japan

^c Chemical Materials Development Department, Global Marketing/R&D Supervisory Department, TANAKA PRECIOUS METAL TECHNOLOGIES Co., Ltd., 22, Wadai, Tsukuba, Ibaraki 300-4247, Japan

Abstract

Thermal decomposition of an organometallic precursor Ru(C₄H₆)(CO)₃^+/0 was observed using gas-phase thermal desorption spectrometry. It was found that the CO ligands were readily released, forming Ru(C₄H₆)⁺ at 600 K. Then, Ru(C₄H₄)⁺ and Ru(C₂H₂)⁺ were produced as a result of sequential H₂ and C₂H₂ release above 800 K. The activation energies of the ligand losses were estimated from the temperature dependences, and were consistent with the available internal energies obtained by DFT calculations. Based on experimental and computational results, Ru(C₄H₄)⁺ was identified as a ruthenium complex with unsubstituted cyclobutadiene, [η⁴-(C₄H₄)Ru]⁺. For the thermal decomposition of neutral Ru(C₄H₆)(CO)₃, the appearance of photoionized Ru(C₄H₆)(CO) is evidence of CO loss from Ru(C₄H₆)(CO)₂ at 740 K. The decomposition further proceeds above 800 K, forming Ru(C₄H₆).

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Article information

DOI: https://doi.org/10.1039/D5CP00200A
Article type: Paper
Submitted: 15 led 2025
Accepted: 08 dub 2025
First published: 08 dub 2025
This article is Open Access

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Phys. Chem. Chem. Phys., 2025,27, 9244-9251

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Decomposition of organometallic precursor tricarbonyl(trimethylenemethane)ruthenium Ru(C₄H₆)(CO)₃^+/0 in the gas phase investigated by thermal desorption spectrometry

K. Miyajima, T. Nagata, F. Mafuné, T. Tsugawa and R. Harada, Phys. Chem. Chem. Phys., 2025, 27, 9244 DOI: 10.1039/D5CP00200A

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