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Spectroscopic Identification of a Bidentate Binding Motif in the Anionic Magnesium-CO2 Complex ([ClMgCO2])

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http://pubman.mpdl.mpg.de/cone/persons/resource/persons85129

Esser,  Tim
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons130085

Knorke,  Harald
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21548

Gewinner,  Sandy
Molecular Physics, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons22079

Schöllkopf,  Wieland
Molecular Physics, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21611

Heine,  Nadja
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Citation

Miller, G. B. S., Esser, T., Knorke, H., Gewinner, S., Schöllkopf, W., Heine, N., et al. (2014). Spectroscopic Identification of a Bidentate Binding Motif in the Anionic Magnesium-CO2 Complex ([ClMgCO2]). Angewandte Chemie, 126(52), 14635-14638. doi:10.1002/ange.201409444.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0023-EDCE-8
Abstract
A magnesium complex incorporating a novel metal-CO2 binding motif is spectroscopically identified. Here we show with the help of infrared photodissociation spectroscopy that the complex exists solely in the [ClMg(η2-O2C)] form. This bidentate double oxygen metal–CO2 coordination has previously not been observed in neutral nor in charged unimetallic complexes. The antisymmetric CO2 stretching mode in [ClMg(η2-O2C)] is found at 1128 cm−1, which is considerably redshifted from the corresponding mode in bare CO2 at 2349 cm−1, suggesting that the CO2 moiety has a considerable negative charge (∼1.8 e ). We also employed electronic structure calculations and kinetic analysis to support the interpretation of the experimental results.