Selective reduction of CO2 to a tantalum formate complex and release of methyl formate from the tantalum(V) center
A cyclometalated NHC-coordinated hydrido tantalum alkoxide was found to selectively react with CO2 to afford the genuine tantalum formate (NHC)(HCOO)Ta(ORF)3 with ORF = OC(CF3)2CH3. In the solid state, the presence of a κ2-O,O-formate moiety was established by single-crystal X-ray diffraction and AT...
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| Hauptverfasser: | , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
November 5, 2021
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| In: |
Inorganic chemistry
Year: 2021, Jahrgang: 60, Heft: 23, Pages: 18291-18295 |
| ISSN: | 1520-510X |
| DOI: | 10.1021/acs.inorgchem.1c02913 |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.inorgchem.1c02913
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| Verfasserangaben: | Jean-Marc Mörsdorf and Joachim Ballmann |
| Zusammenfassung: | A cyclometalated NHC-coordinated hydrido tantalum alkoxide was found to selectively react with CO2 to afford the genuine tantalum formate (NHC)(HCOO)Ta(ORF)3 with ORF = OC(CF3)2CH3. In the solid state, the presence of a κ2-O,O-formate moiety was established by single-crystal X-ray diffraction and ATR-IR spectroscopy, while NMR experiments and DFT modeling studies suggest that the κ1-O-coordination mode is preferred in solution. Despite the accessibility of the latter κ1-O-formate in solution, no over-reduction to a dinuclear methylene diolate was observed. Upon treatment with MeOTf, the κ1-O-formate was methylated selectively, which led to the formation of a tantalum triflate complex along with methyl formate. This is a rare example in which a value-added oxygen-containing organic product (here HCOOMe) is released from an oxophilic early transition metal (here TaV). |
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| Beschreibung: | Gesehen am 22.03.2022 Im Titel ist die Zahl "2" nach "CO" tiefgestellt |
| Beschreibung: | Online Resource |
| ISSN: | 1520-510X |
| DOI: | 10.1021/acs.inorgchem.1c02913 |