Carbon Dioxide Activation by a Palladium Terminal Imido Complex
Stephen J. Goodner A , Annette Grünwald A , Frank W. Heinemann A and Dominik Munz A BA Friedrich-Alexander-Universität Erlangen-Nürnberg, Department of Chemistry and Pharmacy, Institute for General and Inorganic Chemistry, Egerlandstraße 1, 91058 Erlangen, Germany.
B Corresponding author. Email: dominik.munz@fau.de
Australian Journal of Chemistry 72(11) 900-903 https://doi.org/10.1071/CH19323
Submitted: 15 July 2019 Accepted: 09 August 2019 Published: 12 September 2019
Abstract
We recently reported the first example of a palladium(ii) terminal imido complex. We proposed that this complex features exceptional high nucleophilicity at the nitrogen atom and a peculiar zwitterionic electronic structure with an anti-bonding highest-occupied molecular orbital (HOMO). This complex swiftly activated moderately acidic CH, OH, and NH bonds and also reacted with dihydrogen. However, unambiguous nucleophilic reactivity with substrates not featuring a hydrogen atom could not be observed. Herein, we now show that this nucleophilic complex also reacts with CO2 to give a ring-strained four-membered palladium(ii) carbamate complex. Remarkably, the same product is obtained in the reaction of the related bisamido complex, albeit at a slower reaction rate. Density functional theory calculations indicate that the addition of CO2 does not proceed via initial 1,2-addition across the Pd–N bond, but instead through nucleophilic attack by the imido (amido respectively) nitrogen atom.
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