Metal–Ligand Cooperation in Dihydrogen Activation by a Cationic Metallogermylene: Enhanced Activity from Tungsten to Molybdenum
Dihydrogen activation by metallogermylenes was investigated experimentally and theoretically. A neutral NHC-coordinated chlorometallogermylene was synthesized and converted to a cationic base-free metallogermylene of molybdenum via chloride abstraction. The cationic molybdogermylene showed enhanced...
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2024-12-01
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| Online Access: | https://www.mdpi.com/1420-3049/29/24/5974 |
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| author | Rikiya Matsumoto Koichi Nagata Ryo Nakamura Takahito Watanabe Hisako Hashimoto |
| author_facet | Rikiya Matsumoto Koichi Nagata Ryo Nakamura Takahito Watanabe Hisako Hashimoto |
| author_sort | Rikiya Matsumoto |
| collection | DOAJ |
| description | Dihydrogen activation by metallogermylenes was investigated experimentally and theoretically. A neutral NHC-coordinated chlorometallogermylene was synthesized and converted to a cationic base-free metallogermylene of molybdenum via chloride abstraction. The cationic molybdogermylene showed enhanced reactivity toward H<sub>2</sub> compared to the tungsten analog. The reaction mechanism was investigated by theoretical calculations, which revealed a novel route that proceeds via a new type of metal–ligand cooperative activation between the metal and divalent germanium moiety. The activation energy of this route is much lower than that of the alternative route via an “oxidative addition” type of reaction on the single Ge(II) center, which is generally proposed for organotetrylenes. The features of the frontier orbitals and the origin of the metal effect on the H<sub>2</sub> activation are also described. |
| format | Article |
| id | doaj-art-90f76791ee7544c4a2dea3926417ca3e |
| institution | OA Journals |
| issn | 1420-3049 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj-art-90f76791ee7544c4a2dea3926417ca3e2025-08-20T02:01:15ZengMDPI AGMolecules1420-30492024-12-012924597410.3390/molecules29245974Metal–Ligand Cooperation in Dihydrogen Activation by a Cationic Metallogermylene: Enhanced Activity from Tungsten to MolybdenumRikiya Matsumoto0Koichi Nagata1Ryo Nakamura2Takahito Watanabe3Hisako Hashimoto4Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki, Aoba-ku, Sendai 980-8578, JapanDepartment of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki, Aoba-ku, Sendai 980-8578, JapanDepartment of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki, Aoba-ku, Sendai 980-8578, JapanDepartment of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki, Aoba-ku, Sendai 980-8578, JapanDepartment of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki, Aoba-ku, Sendai 980-8578, JapanDihydrogen activation by metallogermylenes was investigated experimentally and theoretically. A neutral NHC-coordinated chlorometallogermylene was synthesized and converted to a cationic base-free metallogermylene of molybdenum via chloride abstraction. The cationic molybdogermylene showed enhanced reactivity toward H<sub>2</sub> compared to the tungsten analog. The reaction mechanism was investigated by theoretical calculations, which revealed a novel route that proceeds via a new type of metal–ligand cooperative activation between the metal and divalent germanium moiety. The activation energy of this route is much lower than that of the alternative route via an “oxidative addition” type of reaction on the single Ge(II) center, which is generally proposed for organotetrylenes. The features of the frontier orbitals and the origin of the metal effect on the H<sub>2</sub> activation are also described.https://www.mdpi.com/1420-3049/29/24/5974metallotetrylenegermylenedihydrogen activationmetal–ligand cooperation |
| spellingShingle | Rikiya Matsumoto Koichi Nagata Ryo Nakamura Takahito Watanabe Hisako Hashimoto Metal–Ligand Cooperation in Dihydrogen Activation by a Cationic Metallogermylene: Enhanced Activity from Tungsten to Molybdenum Molecules metallotetrylene germylene dihydrogen activation metal–ligand cooperation |
| title | Metal–Ligand Cooperation in Dihydrogen Activation by a Cationic Metallogermylene: Enhanced Activity from Tungsten to Molybdenum |
| title_full | Metal–Ligand Cooperation in Dihydrogen Activation by a Cationic Metallogermylene: Enhanced Activity from Tungsten to Molybdenum |
| title_fullStr | Metal–Ligand Cooperation in Dihydrogen Activation by a Cationic Metallogermylene: Enhanced Activity from Tungsten to Molybdenum |
| title_full_unstemmed | Metal–Ligand Cooperation in Dihydrogen Activation by a Cationic Metallogermylene: Enhanced Activity from Tungsten to Molybdenum |
| title_short | Metal–Ligand Cooperation in Dihydrogen Activation by a Cationic Metallogermylene: Enhanced Activity from Tungsten to Molybdenum |
| title_sort | metal ligand cooperation in dihydrogen activation by a cationic metallogermylene enhanced activity from tungsten to molybdenum |
| topic | metallotetrylene germylene dihydrogen activation metal–ligand cooperation |
| url | https://www.mdpi.com/1420-3049/29/24/5974 |
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