Goodner SJ, Grünwald A, Heinemann FW, Munz D (2019)
Publication Type: Journal article
Publication year: 2019
DOI: 10.1071/CH19323
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.
APA:
Goodner, S.J., Grünwald, A., Heinemann, F.W., & Munz, D. (2019). Carbon Dioxide Activation by a Palladium Terminal Imido Complex. Australian Journal of Chemistry. https://doi.org/10.1071/CH19323
MLA:
Goodner, Stephen J., et al. "Carbon Dioxide Activation by a Palladium Terminal Imido Complex." Australian Journal of Chemistry (2019).
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