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Theoretical study on mechanism of the photochemical ligand substitution of fac-[Re-I(bpy)(CO)(3)(PR3)](+) complex

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タイトル: Theoretical study on mechanism of the photochemical ligand substitution of fac-[Re-I(bpy)(CO)(3)(PR3)](+) complex
著者: Saita, Kenichiro 著作を一覧する
Harabuchi, Yu 著作を一覧する
Taketsugu, Tetsuya 著作を一覧する
Ishitani, Osamu 著作を一覧する
Maeda, Satoshi 著作を一覧する
発行日: 2016年 7月14日
出版者: Royal Society of Chemistry
誌名: Physical chemistry chemical physics
巻: 18
号: 26
開始ページ: 17557
終了ページ: 17564
出版社 DOI: 10.1039/c6cp02314b
抄録: The mechanism of the CO ligand dissociation of fac-[Re-I(bpy)(CO)(3)P(OMe)(3)](+) has theoretically been investigated, as the dominant process of the photochemical ligand substitution (PLS) reactions of fac-[Re-I(bpy)(CO)(3)PR3](+), by using the (TD-)DFT method. The PLS reactivity can be determined by the topology of the T-1 potential energy surface because the photoexcited complex is able to decay into the T-1 state by internal conversions (through conical intersections) and intersystem crossings (via crossing seams) with sufficiently low energy barriers. The T-1 state has a character of the metal-to-ligand charge-transfer ((MLCT)-M-3) around the Franck-Condon region, and it changes to the metal-centered ((MC)-M-3) state as the Re-CO bond is elongated and bent. The equatorial CO ligand has a much higher energy barrier to leave than that of the axial CO, so that the axial CO ligand selectively dissociates in the PLS reaction. The single-component artificial force induced reaction (SC-AFIR) search reveals the CO dissociation pathway in photostable fac-[ReI(bpy)(CO)(3)Cl]; however, the dissociation barrier on the T-1 state is substantially higher than that in fac-[ReI(bpy)(CO)(3)PR3](+) and the minimum-energy seams of crossings (MESXs) are located before and below the barrier. The MESXs have also been searched in fac-[Re-I(bpy)(CO)(3)PR3](+) and no MESXs were found before and below the barrier.
資料タイプ: article (author version)
出現コレクション:雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

提供者: 前田 理


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