Revealing the electron driven mechanism in metal catalyzed Kumada cross coupling reaction
Abstract The electron motion mechanism of the metal-catalyzed Kumada cross-coupling reaction, which synthesizes biphenyl from chlorobenzene and phenylmagnesium chloride (a Grignard reagent) using a palladium (Pd) complex with an auxiliary phosphine ligand, is elucidated. This analysis is grounded in...
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Nature Portfolio
2025-02-01
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| Series: | Scientific Reports |
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| Online Access: | https://doi.org/10.1038/s41598-025-88207-w |
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| author | Noriyuki Takai Takuro Tsutsumi Kenichiro Saita Tetsuya Taketsugu Takao Tsuneda |
| author_facet | Noriyuki Takai Takuro Tsutsumi Kenichiro Saita Tetsuya Taketsugu Takao Tsuneda |
| author_sort | Noriyuki Takai |
| collection | DOAJ |
| description | Abstract The electron motion mechanism of the metal-catalyzed Kumada cross-coupling reaction, which synthesizes biphenyl from chlorobenzene and phenylmagnesium chloride (a Grignard reagent) using a palladium (Pd) complex with an auxiliary phosphine ligand, is elucidated. This analysis is grounded in reactive orbital energy theory (ROET), enabling the examination of electron motions in comprehensive chemical reactions. We first calculated the intrinsic reaction coordinates (IRCs) for the four key processes of this reaction: oxidative addition, transmetalation steps 1 and 2, and reductive elimination. Using automatic orbital tracing in the ROET analysis, we identified the reactive orbitals for these IRCs. Consequently, we revealed the sequential electron motions driving these processes through animations, clarifying the electronic roles of the Pd center, the auxiliary ligand, and the Grignard reagent. These electron motions are consistent with experimental observations, indicating that the electron motions driving metal complex reactions can be effectively represented by changes in a single molecular orbital. |
| format | Article |
| id | doaj-art-bfa8a691eefc49de89f2bc2b6ef5af08 |
| institution | Kabale University |
| issn | 2045-2322 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj-art-bfa8a691eefc49de89f2bc2b6ef5af082025-02-09T12:36:11ZengNature PortfolioScientific Reports2045-23222025-02-0115111110.1038/s41598-025-88207-wRevealing the electron driven mechanism in metal catalyzed Kumada cross coupling reactionNoriyuki Takai0Takuro Tsutsumi1Kenichiro Saita2Tetsuya Taketsugu3Takao Tsuneda4Graduate School of Chemical Sciences and Engineering, Hokkaido UniversityDepartment of Chemistry, Faculty of Science, Hokkaido UniversityDepartment of Chemistry, Faculty of Science, Hokkaido UniversityDepartment of Chemistry, Faculty of Science, Hokkaido UniversityDepartment of Chemistry, Faculty of Science, Hokkaido UniversityAbstract The electron motion mechanism of the metal-catalyzed Kumada cross-coupling reaction, which synthesizes biphenyl from chlorobenzene and phenylmagnesium chloride (a Grignard reagent) using a palladium (Pd) complex with an auxiliary phosphine ligand, is elucidated. This analysis is grounded in reactive orbital energy theory (ROET), enabling the examination of electron motions in comprehensive chemical reactions. We first calculated the intrinsic reaction coordinates (IRCs) for the four key processes of this reaction: oxidative addition, transmetalation steps 1 and 2, and reductive elimination. Using automatic orbital tracing in the ROET analysis, we identified the reactive orbitals for these IRCs. Consequently, we revealed the sequential electron motions driving these processes through animations, clarifying the electronic roles of the Pd center, the auxiliary ligand, and the Grignard reagent. These electron motions are consistent with experimental observations, indicating that the electron motions driving metal complex reactions can be effectively represented by changes in a single molecular orbital.https://doi.org/10.1038/s41598-025-88207-wCross-coupling reactionMetal complex reactionElectronic theoryGrignard reagentDensity functional theoryOrbital energy |
| spellingShingle | Noriyuki Takai Takuro Tsutsumi Kenichiro Saita Tetsuya Taketsugu Takao Tsuneda Revealing the electron driven mechanism in metal catalyzed Kumada cross coupling reaction Scientific Reports Cross-coupling reaction Metal complex reaction Electronic theory Grignard reagent Density functional theory Orbital energy |
| title | Revealing the electron driven mechanism in metal catalyzed Kumada cross coupling reaction |
| title_full | Revealing the electron driven mechanism in metal catalyzed Kumada cross coupling reaction |
| title_fullStr | Revealing the electron driven mechanism in metal catalyzed Kumada cross coupling reaction |
| title_full_unstemmed | Revealing the electron driven mechanism in metal catalyzed Kumada cross coupling reaction |
| title_short | Revealing the electron driven mechanism in metal catalyzed Kumada cross coupling reaction |
| title_sort | revealing the electron driven mechanism in metal catalyzed kumada cross coupling reaction |
| topic | Cross-coupling reaction Metal complex reaction Electronic theory Grignard reagent Density functional theory Orbital energy |
| url | https://doi.org/10.1038/s41598-025-88207-w |
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