令和4年度 京都大学化学研究所 スーパーコンピュータシステム 利用報告

Sameera, W. M. C.

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RIGHT:URL:CITATION:AUTHOR(S):ISSUE DATE:TITLE:COが配位した生体模倣型[MoSM](M = Fe, Co, Ni)クラスター錯体の理論計算Sameera, W. M. C.Sameera, W. M. C.. COが配位した生体模倣型[MoSM] (M = Fe, Co, Ni)クラスター錯体の理論計算. 京都大学化学研究所スーパーコンピュータシステム研究成果報告書 2023, 2022:18-182023-03http://hdl.handle.net/2433/283140令和４年度   京都大学化学研究所 スーパーコンピュータシステム 利用報告書  CO が配位した生体模倣型[Mo3S4M] (M = Fe, Co, Ni)クラスター錯体の理論計算 CO-Bound Biomimetic [Mo3S4M] (M = Fe, Co, Ni) Clusters: A Computational Study  University of Colombo         W. M. C. Sameera    研究成果概要  Transition metal clusters can be used as catalysts to perform chemically or biologically relevant reactions.1,2 Relationships between the electronic structure and reactivity can be established by employing density functional theory (DFT). We have developed [Mo3S4M]-type clusters (M = Fe, Co, Ni), consisting bulky cyclopentadienyl ligands (CpXL, C5Me4SiEt3). CO can be coordinated to [Mo3S4M] cubes. According to experimental data, [CpXL3Mo3S4M(CO)]+ (M = Co, Ni) is stable, while [CpXL3Mo3S4Fe(CO)]+ complex revealed unexpected instability. Their M-CO interactions were analyzed by DFT calculations.  An energy decomposition analysis (EDA) together with the natural orbitals for chemical valence (NOCV) was performed to rationalize the M-CO interactions. The interaction energy between M and CO follows the order of Fe-CO (-101.1 kcal/mol) > Co-CO (-81.5 kcal/mol) > Ni-CO (-77.3 kcal/mol). In all three cases, orbital interactions become dominant compared to electrostatic, dispersion, and solvent interactions. According to EDA-NOCV, π back-donation from Co to π*(CO) is stronger than 𝜎𝜎 CO to M(d) 𝜎𝜎 donation for all three systems. These findings give quantitative insights to develop bio-mimetic catalysts for the direct conversion of CO into hydrocarbons.   発表論文（謝辞あり） (1) Y. Ohki, K. Munakata, R. Hara, M. Kachi, K. Uchida, M. Tada, R. E. Cramer, W. M. C. Sameera, T. Takayama, Y. Sakai, S. Kuriyama, Y. Nishibayashi, K. Tanifuji, “Nitrogen reduction by the Fe sites of synthetic [Mo3S4Fe] cubes”, Nature, 607, 86-90 (2022). (2) W. M. C. Sameera, Y. Takeda, Y. Ohki, “Transition Metal Catalyzed Cross-coupling and Nitrogen Reduction Reactions: Lessons from Computational Studies”, Adv. Organomet. Chem., 78, 35-78 (2022). (3) K. Tanifuji, Y. Sakai, Y. Matsuoka, M. Tada, W. M. C. Sameera, Y. Ohki, “CO Binding onto Heterometals of [Mo3S4M] (M = Fe, Co, Ni) Cubes”, Bull. Chem. Soc. Jpn., 95, 1190-1195 (2022). - 18 -

CO-Bound Biomimetic [Mo₃S₄M] (M = Fe, Co, Ni) Clusters: A Computational Study

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CO-Bound Biomimetic [Mo₃S₄M] (M = Fe, Co, Ni) Clusters: A Computational Study

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