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

Nitrenium ion species are examined using computational methods (DFT, MP2, coupled-cluster, and a composite method, CBS-APNO) with a particular emphasis on non-aromatic species (i.e. those lacking an aromatic or heteroaromatic ring in direct conjugation with the formal nitrenium ion center.) Substitution of the N+ center with alkyl, alkoxy, vinyl, acyl, sulfonyl, among others, were 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. And, to the extent the singlet states could be characterized as discrete minima on the PES, (2) the effect of the substituents on singlet-triplet energy splitting as well as (3) the relative stabilities of the nitrenium ions as defined by N-hydration enthalpies (RR’N+ + H¬2O -> RR’NOH¬2+). Nearly all simple alkyl and di-alkyl nitrenium ion singlet states are predicted to rearrange without detectable barriers, largely through 1,2 H or alkyl shifts. Methyl and N-N-dimethylnitrenium ion singlet states could be characterized as formal minima on the PES. However these species show small or insignificant barriers to isomerization. Disubstituted nitrenium ions that include an alkyl group and a conjugating substituent such as alkoxyl, vinyl or phenyl, show meaningful barriers to isomerization and are thus predicted to possess non-trivial lifetimes in solution. Alkyl groups substantially stabilize the singlet state relative to the situation in the parent nitrenium ion NH¬2+ To the point where the two states are nearly degenerate. Other groups that interact with the nitrenium ion center decrease DEst in the order formoyl< vinyl < phenyl < alkoxy ~sulfonyl < cyclopropyl ~ cyclobutyl. The latter two substituents interact strongly with the (singlet) nitrenium ion center through the formation of non-classical bonding reminiscent of the bisected cyclopropylcarbinyl ion case for carbocations. When singlet state stability is evaluated in the context of N-hydration enthalpies, it is found that the ordering is acyl