Abstract

Nitro compounds in the triplet state are strong oxidizing agents, one of the reactions of which is the excited-state hydrogen atom transfer. The energy characteristics of the reaction of triplet nitromethane with methylamine are obtained using ab-initio methods. MP2 and CASSCF methods were used. Calculated atomic charges has shown that the transfer of a proton must be accompanied by a simultaneous transfer of an electron. Optimization of the reaction complexes showed that in the course of the reaction there is a change in the reaction coordinate. The first stage is a rotation of methylamine molecule and the second stage is a lengthening of the C-H bond. Energetic and geometric parameters calculated by the MP2 and CASSCF methods are very close to each other which means the possibility of using the MP2 method for modeling similar processes as the main one.

Highlights

  • Due to the close arrangement of the singlet and triplet electronic levels in the nitro compounds (NC), the intersystem crossing (ISC) probability increases significantly compared with other organic compounds [1]

  • The first equation presents the NC internal conversion followed by ISC

  • The process of hydrogen transfer between triplet nitromethane and methyl group of methylamine was the point of interest

Read more

Summary

Introduction

Due to the close arrangement of the singlet and triplet electronic levels in the nitro compounds (NC), the intersystem crossing (ISC) probability increases significantly compared with other organic compounds [1]. It is known that the quantum yield of the triplet state in NB reaches 0.67 [2]. Such tendency is typical for all NC: both aliphatic and aromatic [2,3]. The chemical reactivity of triplet NC differs with singlet ones. They are able to transfer hydrogen from various compounds, including alcohols and amines [4,5,6,7]. After pre-reaction complex formation hydrogen transfer takes place. The following process takes place after NC gains the second hydrogen atom. We decide to investigate this process, especially the second reaction with hydrogen transfer

Methods
Discussion
Conclusion

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.