Facile Deoxygenative Reduction of a Bridging Carbonato Ligand with Silyl and Boryl 4,4’‐Bipyridinylidene Reagents

The reactivity of CO2 with a previously described PCcarbeneP cobalt(I) hydroxide is reported. Insertion of CO2 into the Co−OH bond followed by a dehydration reaction releasing water results in a cobalt(I) bridging carbonate species featuring fluctional κ1: κ1 and κ1: κ2 coordination of the central c...

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Bibliographic Details
Published in:Zeitschrift für anorganische und allgemeine Chemie (1950) 2023-02, Vol.649 (4), p.n/a
Main Authors: Clapson, Marissa L., Dubrawski, Zachary S., Piers, Warren E., Gelfand, Benjamin S.
Format: Article
Language:English
Subjects:
Carbon dioxide
carbon dioxide activation
carbonate reduction
Cobalt
Dehydration
Deoxygenation
pincer ligands
Reagents
Reducing agents
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Summary:The reactivity of CO2 with a previously described PCcarbeneP cobalt(I) hydroxide is reported. Insertion of CO2 into the Co−OH bond followed by a dehydration reaction releasing water results in a cobalt(I) bridging carbonate species featuring fluctional κ1: κ1 and κ1: κ2 coordination of the central carbonate moiety. The reduction chemistry of the resulting cobalt(I) bridging carbonate species is explored utilizing deoxygenative reducing agents N,N′‐bis(trimethylsilyl)‐ and N,N′‐bis(pinacolatoboryl)‐4,4′‐bipyridinylidene. The three‐electron reduction produces the corresponding PCcarbeneP cobalt(I) siloxide or boroxide complex alongside a PCcarbeneP cobalt(0) monocarbonyl, silyl/boryl ether, and 4,4’‐bipyridine.
ISSN:0044-2313
1521-3749
DOI:10.1002/zaac.202200272