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Stepwise Reduction of an α‐Phosphonio–Carbocation to a Crystalline Phosphorus Radical Cation and an Acridinyl–Phosphorus Ylide
Author(s) -
Hudnall Todd W.,
Dorsey Christopher L.,
Jones James S.,
Gabbaï François P.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201504744
Subject(s) - carbocation , ylide , chemistry , phosphorus , population , inorganic chemistry , photochemistry , medicinal chemistry , organic chemistry , demography , sociology
We have synthesized the dicationic α‐phosphonio–carbocation 1 2+ , which can be regarded as a two‐electron oxidized phosphorus ylide. Carbocation 1 2+ exhibits two reversible reduction waves at −0.28 and −0.90 V (vs. Fc + /Fc) indicating that both the radical cation 1 . + and the neural phosphorus ylide 1 can be generated. Indeed, reduction of 1 2+ with Zn afforded 1 . + as a dark green solid that was characterized by XRD and EPR spectroscopy, and reduction with Mg(Ant)⋅(THF) 3 gave 1 , which was characterized by 1 H and 31 P NMR spectroscopy. Computational analyses reveal the stepwise population of a C−P π bonding orbital upon reduction of 1 2+ .