Next Article in Journal
Core-Shell Nanoencapsulation of α-Tocopherol by Blending Sodium Oleate and Rebaudioside A: Preparation, Characterization, and Antioxidant Activity
Next Article in Special Issue
Do Osmolytes Impact the Structure and Dynamics of Myoglobin?
Previous Article in Journal
Molecular Mechanism of Action of RORγt Agonists and Inverse Agonists: Insights from Molecular Dynamics Simulation
Previous Article in Special Issue
Excited State Structural Evolution of a GFP Single-Site Mutant Tracked by Tunable Femtosecond-Stimulated Raman Spectroscopy
Article Menu

Export Article

Open AccessArticle
Molecules 2018, 23(12), 3182; https://doi.org/10.3390/molecules23123182

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

1,2,†
,
1,†
,
1
,
1,3
and
1,*
1
Department of Chemistry, The University of Hong Kong, Hong Kong S.A.R., China
2
Institute of Life Sciences, Jiangsu University, Zhenjiang 212013, China
3
School of Physical Science and Technology, Shanghai Tech University, Shanghai 201210, China
These authors contributed equally to this work.
*
Author to whom correspondence should be addressed.
Academic Editor: Chong Fang
Received: 8 November 2018 / Revised: 26 November 2018 / Accepted: 30 November 2018 / Published: 3 December 2018
(This article belongs to the Special Issue Vibrational Probes of Biomolecular Structure and Dynamics)
Full-Text   |   PDF [1650 KB, uploaded 3 December 2018]   |  

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 BF4 (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 H2O 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 H2O. 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. View Full-Text
Keywords: nitrenium ion; resonance Raman; transient absorption; reactive intermediate nitrenium ion; resonance Raman; transient absorption; reactive intermediate
Figures

Graphical abstract

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

Supplementary material

SciFeed

Share & Cite This Article

MDPI and ACS Style

Du, L.; Lan, X.; Yan, Z.; Zhu, R.; Phillips, D.L. Time-Resolved Spectroscopic Study of N,N-Di(4-bromo)nitrenium Ions in Selected Solutions. Molecules 2018, 23, 3182.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Molecules EISSN 1420-3049 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top