Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds
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Author(s)
García-Iriepa, Cristina
Temprado, Manuel
Transue, Wesley
Velian, Alexandra
Nava, Matthew Jordan
Cummins, Christopher C
Alternative Title
Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds
Date Issued
August 2017
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Transue, Wesley J. et al. “Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-Phosphanorbornadiene Compounds.” Journal of the American Chemical Society 139, 31 (July 2017): 10822–10831 © 2017 American Chemical Society
Version
Original manuscript
Abstract
Dibenzo-7-phosphanorbornadiene compounds, RPA (A = C₁₄H₁₀ 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, [Me₂N═P]. Kinetic investigations of iPr₂NPA thermolysis in 1,3-cyclohexadiene and/or benzene-d₆ are consistent with a model of unimolecular fragmentation to yield free phosphinidene [iPr₂N═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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jacs.7b05464
