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Journal Article

Bis[(dialkylamino)cyclopropenimine]-Stabilized PIII- and PV-Centered Dications


Kozma,  Ágnes
Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society;


Rust,  Jörg
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;


Alcarazo,  Manuel
Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Kozma, Á., Rust, J., & Alcarazo, M. (2015). Bis[(dialkylamino)cyclopropenimine]-Stabilized PIII- and PV-Centered Dications. Chemistry – A European Journal, 21(30), 10829-10834. doi:10.1002/chem.201500688.

Cite as: http://hdl.handle.net/11858/00-001M-0000-0028-1849-B
The treatment of bis[(dialkylamino)cyclopropenimines] with dihalophosphines in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) to form diimine-stabilized PIII-centered dications is reported. The structures of the new compounds were determined by using X-ray diffraction analysis and their donor abilities as ligands evaluated through electrochemical methods. Despite the two positive charges that they bear, these compounds depict intermediate behavior between that of phosphines and phosphites. The coordination of the [L2PR]2+ moiety to AuI and AgI is also reported. Even more surprisingly, these phosphorus centers can be oxidized to the corresponding PV dications in the presence of strong oxidants such as peroxides or XeF2.