Discrete Existence of Singlet Nitrenium Ions Revisited: Computational Studies of Non-Aryl Nitrenium Ions and Their Rearrangements.

ABSTRACT: Nitrenium ion species are examined using computational methods (DFT, MP2, coupled-cluster, and a composite method, CBS-APNO) with a particular emphasis on nonaromatic species (i.e., those lacking an aromatic or heteroaromatic ring in direct conjugation with the formal nitrenium ion center.) The substitution of the N⁺ center with alkyl, alkoxy, vinyl, acyl, and sulfonyl, among others, was evaluated. For these species, three properties are considered. (1) The stability of the nitrenium ions to unimolecular isomerizations such as 1,2 alkyl or H shifts; to the extent that the singlet states could be characterized as discrete minima on the potential energy surface (PES), (2) the effect of the substituents on singlet-triplet energy splitting as well as (3) the relative stabilities of

SUBMITTER: Falvey DE 

PROVIDER: S-EPMC6645317 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature