title: Ylidic radical-molecule reactions.
abstract: The known reactions between a neutral radical and a neutral closed-shell sigma-type molecule are generally associated with the atom/group-abstraction (e.g., CN, OH reactions) or the carbenoid insertion processes (e.g., CH reactions). In this article, we describe a new type of neutral radical-molecule reaction that feature the nucleophilic addition and elimination mechanism based on the systematic Gaussian-3//MP2(full)/6-31G(d) investigations on the PH(3)CH+HX model reactions (X = CH(3), NH(2), OH, F, CH(2)F, CHF(2), CF(3), NHCH(3)/CH(2)NH(2), OCH(3)/CH(2)OH). The novel properties are found to benefit both from the radical and ylidic characters of PH(3)CH, and the type of reagent HX determines the nucleophilic addition reactivity. The present work is the first study on the chemical reactivity of the ylidic radicals.
authors.affiliation: State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
authors.forename: Hong-Bin
authors.initials: HB
authors.lastname: Xie
authors.forename: Yi-Hong
authors.initials: YH
authors.lastname: Ding
authors.forename: Chia-Chung
authors.initials: CC
authors.lastname: Sun
mesh_terms: D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry; D006838:Hydrocarbons / Q000737:chemistry; D008956:Models, Chemical; D010720:Phosphines / Q000737:chemistry*
chemical_list: D005609:Free Radicals; D006838:Hydrocarbons; D010720:Phosphines