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Spectroscopic Identification of a Bidentate Binding Motif in the Anionic Magnesium–CO 2 Complex ([ClMgCO 2 ] − )
Author(s) -
Miller Glenn B. S.,
Esser Tim K.,
Knorke Harald,
Gewinner Sandy,
Schöllkopf Wieland,
Heine Nadja,
Asmis Knut R.,
Uggerud Einar
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201409444
Subject(s) - denticity , chemistry , magnesium , metal , photodissociation , moiety , infrared spectroscopy , infrared , crystallography , photochemistry , stereochemistry , crystal structure , physics , organic chemistry , optics
A magnesium complex incorporating a novel metal–CO 2 binding motif is spectroscopically identified. Here we show with the help of infrared photodissociation spectroscopy that the complex exists solely in the [ClMg(η 2 ‐O 2 C)] − form. This bidentate double oxygen metal–CO 2 coordination has previously not been observed in neutral nor in charged unimetallic complexes. The antisymmetric CO 2 stretching mode in [ClMg(η 2 ‐O 2 C)] − is found at 1128 cm −1 , which is considerably redshifted from the corresponding mode in bare CO 2 at 2349 cm −1 , suggesting that the CO 2 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.