Reactivity of Frustrated Lewis Pair: Carbocation versus Radical Intermediates.
Chemistry
; 30(11): e202303901, 2024 Feb 21.
Article
in En
| MEDLINE
| ID: mdl-38116858
ABSTRACT
Recent reports of radical formation within frustrated Lewis pairs (FLPs) suggested that single-electron transfer (SET) could play an important role in their chemistry especially for C-C coupling. In sharp contrast, our extensive dispersion-corrected DFT calculations show that although reactive benzhydryl radical along with phosphine radical cation species can be kinetically generated from bulky phosphines and benzhydryl cation, direct P-C hetero-coupling may lead to bulky phosphonium cation as reactive carbocation transfer reagents to styrene substrates, which is kinetically much more favorable than the recently proposed radical C-C coupling between benzhydryl radical and styrene. Similarly, meta-stable radical cation Mes3 P+ â
salt is also kinetically accessible via SET reactions of Mes3 P and B(C6 F5 )3 with 0.5 equivalent of p-O2 C6 Cl4 .
Full text:
1
Database:
MEDLINE
Language:
En
Journal:
Chemistry
Journal subject:
QUIMICA
Year:
2024
Type:
Article
Affiliation country:
Germany