0000000001300486
AUTHOR
Paul D. Boyle
Phosphorus-Chalcogen Ring Expansion and Metal Coordination
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…
Trapping Rare and Elusive Phosphinidene Chalcogenides
Four-membered rings with a P2Ch2 core (Ch=S, Se) and phosphorus in the +3 oxidation state have been synthesized. The utility of these rings as a source of monomeric phosphinidene chalcogenides was probed by the addition of an N-heterocyclic carbene, resulting in a base-stabilized phosphinidene sulfide. Similarly, persistence of the phosphinidene selenide in solution was shown through cycloaddition chemistry with 2,3-dimethylbutadiene at elevated temperatures. The observed reactivity was explained by detailed computational work that established the conditions upon which the P2Ch2 rings can liberate phosphinidene chalcogenides. peerReviewed
CCDC 1569579: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1485222: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Taylor E. Pritchard, Paul D. Boyle, Juuso Valjus, Heikki M. Tuononen, Paul J. Ragogna|2017|Angew.Chem.,Int.Ed.|56|6236|doi:10.1002/anie.201611196
CCDC 1569581: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1569577: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1485220: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Taylor E. Pritchard, Paul D. Boyle, Juuso Valjus, Heikki M. Tuononen, Paul J. Ragogna|2017|Angew.Chem.,Int.Ed.|56|6236|doi:10.1002/anie.201611196
CCDC 1569578: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1485223: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Taylor E. Pritchard, Paul D. Boyle, Juuso Valjus, Heikki M. Tuononen, Paul J. Ragogna|2017|Angew.Chem.,Int.Ed.|56|6236|doi:10.1002/anie.201611196
CCDC 1569582: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1569580: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Juuso Valjus, Taylor E. Pritchard, Paul D. Boyle, Heikki M. Tuononen, Paul J. Ragogna|2017|Inorg.Chem.|56|13500|doi:10.1021/acs.inorgchem.7b02217
CCDC 1485221: Experimental Crystal Structure Determination
Related Article: Cameron M. E. Graham, Taylor E. Pritchard, Paul D. Boyle, Juuso Valjus, Heikki M. Tuononen, Paul J. Ragogna|2017|Angew.Chem.,Int.Ed.|56|6236|doi:10.1002/anie.201611196