Hydrophosphination of alkene and alkyne substrates with primary phosphines under mild conditions proceeds with a zirconium catalyst, [κ5-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH]Zr in the presence of light. Catalysis ensues rapidly with an array of activated and unactivated substrates, including α-olefins, to provide exclusively secondary phosphines in minutes to hours. Dienes and diynes undergo each an intermolecular and an intramolecular hydrophosphination event to furnish cyclic phosphines. The catalytically active, fluorescent zirconium-phosphido compound promotes hydrophosphination under either ultraviolet or visible light. Investigation of the effect of light on catalysis by spectroscopic and computational methods suggests that a charge transfer event is responsible for turnover.

Light-dependent, zirconium-catalyzed hydrophosphination

255th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.