Selective reduction of CO2 to a tantalum formate complex and release of methyl formate from the tantalum(V) center

• Verfasst von: Mörsdorf, Jean-Marc [VerfasserIn]
• Verfasst von: Ballmann, Joachim [VerfasserIn]
• Titel: Selective reduction of CO2 to a tantalum formate complex and release of methyl formate from the tantalum(V) center
• Verf.angabe: Jean-Marc Mörsdorf and Joachim Ballmann
• E-Jahr: 2021
• Jahr: November 5, 2021
• Umfang: 5 S.
• Fussnoten: Gesehen am 22.03.2022 ; Im Titel ist die Zahl "2" nach "CO" tiefgestellt
• Titel Quelle: Enthalten in: Inorganic chemistry
• Ort Quelle: Washington, DC : American Chemical Society, 1962
• Jahr Quelle: 2021
• Band/Heft Quelle: 60(2021), 23, Seite 18291-18295
• ISSN Quelle: 1520-510X
• DOI: doi:10.1021/acs.inorgchem.1c02913
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1796296279

Abstract

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).