Phosphorus-Chalcogen Ring Expansion and Metal Coordination
Graham, C. M. E., Valjus, J., Pritchard, T. E., Boyle, P. D., Tuononen, H., & Ragogna, P. J. (2017). Phosphorus-Chalcogen Ring Expansion and Metal Coordination. Inorganic Chemistry, 56 (21), 13500-13509. doi:10.1021/acs.inorgchem.7b02217
Published inInorganic Chemistry
DisciplineEpäorgaaninen ja analyyttinen kemia
© 2017 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
The reactivity of 4-membered (RPCh)2 rings (Ch = S, Se) that contain phosphorus in the +3 oxidation state is reported. These compounds undergo ring expansion to (RPCh)3 with the addition of a Lewis base. The 6-membered rings were found to be more stable than the 4-membered precursors, and the mechanism of their formation was investigated experimentally and by density functional theory calculations. The computational work identified two plausible mechanisms involving a phosphinidene chalcogenide intermediate, either as a free species or stabilized by a suitable base. Both the 4- and 6-membered rings were found to react with coinage metals, giving the same products: (RPCh)3 rings bound to the metal center from the phosphorus atom in tripodal fashion.