Phosphorus-Chalcogen Ring Expansion and Metal Coordination

Graham, Cameron M. E.; Valjus, Juuso; Pritchard, Taylor E.; Boyle, Paul D.; Tuononen, Heikki; Ragogna, Paul J.

doi:10.1021/acs.inorgchem.7b02217

Final Draft

Katso/Avaa

1.6 Mb

Lataukset:

Show download details Hide download details

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. https://doi.org/10.1021/acs.inorgchem.7b02217

Julkaistu sarjassa

Inorganic Chemistry

Tekijät

Graham, Cameron M. E. |

Valjus, Juuso |

Pritchard, Taylor E. |

Boyle, Paul D. |

Tuononen, Heikki |

Ragogna, Paul J.

Päivämäärä

2017

Oppiaine

Fysikaalinen kemia Nanoscience Center Physical Chemistry Nanoscience Center

Tekijänoikeudet

© 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.

Julkaisija

American Chemical Society

ISSN Hae Julkaisufoorumista

0020-1669