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Time-Resolved Spectroscopic Study of N,N-Di(4-bromo)nitrenium Ions in Selected Solutions.

ABSTRACT: Nitrenium ions are important reactive intermediates in chemistry and biology. In this work, femtosecond and nanosecond transient absorption (fs-TA and ns-TA) along with nanosecond time-resolved resonance Raman (ns-TR³) experiments were employed to examine the photochemical pathways of N-(4,4'-dibromodiphenylamino)-2,4,6-trimethylpyridinium BF?^- (salt (DN) from just absorption of a photon of light to the production of the important N,N-di(4-bromophenyl)nitrenium ion 2. In acetonitrile (MeCN), the formation of halogenated diarylnitrenium ion 2 was observed within 4 ps, showing the vibrational spectra with strong intensity. The nucleophilic adduct reaction of ion 2 with H?O was also examined in aqueous solutions. The direct detection of the unique ortho adduct intermediate 3 shows that there is an efficient and exclusive reaction pathway for 2 with H?O. The results shown in this paper give new characterization of 2, which can be used to design time-resolved spectroscopy investigations of covalent addition reactions of nitrenium ions with other molecules in future studies.

SUBMITTER: Du L

PROVIDER: S-EPMC6321521 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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Time-Resolved Spectroscopic Study of N,N-Di(4-bromo)nitrenium Ions in Selected Solutions.

Du Lili L Lan Xin X Yan Zhiping Z Zhu Ruixue R Phillips David Lee DL

Molecules (Basel, Switzerland) 20181203 12

Nitrenium ions are important reactive intermediates in chemistry and biology. In this work, femtosecond and nanosecond transient absorption (fs-TA and ns-TA) along with nanosecond time-resolved resonance Raman (ns-TR³) experiments were employed to examine the photochemical pathways of N-(4,4'-dibromodiphenylamino)-2,4,6-trimethylpyridinium BF₄- (salt (DN) from just absorption of a photon of light to the production of the important N,N-di(4-bromophenyl)nitrenium io ...[more]

PMID: 30513911

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Project description: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 the nitrenium ions as defined by N-hydration enthalpies (RR'N+ + H2O → RR'NOH2 +). 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 nontrivial lifetimes in solution. Alkyl groups substantially stabilize the singlet state relative to the situation in the parent nitrenium ion NH2 + to the point where the two states are nearly degenerate. Other groups that interact with the nitrenium ion center decrease the ΔE st 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 a nonclassical 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 < vinyl < alkoxyl < phenyl < cyclopropyl and cyclobutyl.

Dataset Information

Time-Resolved Spectroscopic Study of N,N-Di(4-bromo)nitrenium Ions in Selected Solutions.

Publications

Time-Resolved Spectroscopic Study of <i>N</i>,<i>N</i>-Di(4-bromo)nitrenium Ions in Selected Solutions.

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