2017/07/13 by Wesley J. Transue, Alexandra Velian, Matthew Nava +3 · 1 citation
Chemistry · #Synthesis and characterization of novel inorganic/organometallic compounds #Organometallic Complex Synthesis and Catalysis #Organophosphorus compounds synthesis
paper · doi:10.1021/jacs.7b05464
openalex publication_date 2017/07/13 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30
Dibenzo-7-phosphanorbornadiene compounds, RP A ( A = C 14 H 10 or anthracene), are investigated as phosphinidene sources upon thermally induced (70–90 °C) anthracene elimination. Analysis of substituent effects reveals that π-donating dialkylamide groups are paramount to successful phosphinidene transfer; poorer π-donors give reduced or no transfer. Substituent steric bulk is also implicated in successful transfer. Molecular beam mass spectrometry (MBMS) studies of each derivative reveal dialkylamide derivatives to be promising precursors for further gas-phase spectroscopic studies of phosphinidenes; in particular, we present evidence of direct detection of the dimethylamide derivative, [Me 2 N═P]. Kinetic investigations of i Pr 2 NP A thermolysis in 1,3-cyclohexadiene and/or benzene- d 6 are consistent with a model of unimolecular fragmentation to yield free phosphinidene [ i Pr 2 N═P] as a transient reactive intermediate. This conclusion is probed by density functional theory (DFT) calculations, which favored a mechanistic model featuring free singlet aminophosphinidenes. The breadth of phosphinidene acceptors is expanded to unsaturated substrates beyond 1,3-dienes to include olefins and alkynes; this provides a new synthetic route to valuable amino-substituted phosphiranes and phosphirenes, respectively. Stereoselective phosphinidene transfer to olefins is consistent with singlet phosphinidene reactivity by analogy with the Skell hypothesis for singlet carbene addition to olefins.