[3 + 2] versus [2 + 2] Addition: A Density Functional Theory Study on the Mechanistic Aspects of Transition Metal-Assisted Formation of 1,2-Dinitrosoalkanes
Joint Authors
Opoku, Ernest
Tia, Richard
Adei, Evans
Source
Issue
Vol. 2016, Issue 2016 (31 Dec. 2016), pp.1-10, 10 p.
Publisher
Hindawi Publishing Corporation
Publication Date
2016-12-25
Country of Publication
Egypt
No. of Pages
10
Main Subjects
Abstract EN
The pathways for the transition metal-assisted formation of 1,2-dinitrosoalkane complexes of cobalt and its congeners, have been studied using DFT/M06 with the LACVP* basis set.
The activation barriers for the one-step [3 + 2] addition pathway for the formation of 1,2-dinitrosoalkanes, proposed by Bergman and Becker, are generally low compared to the activation barriers for the [2 + 2] addition to form an intermediate, which is the first of the two-step pathway proposed by Rappé and Upton, which are very high.
The barriers of the rearrangement of the Rappé intermediates to the final products by reductive elimination involving the second metal-nitrogen π-bond are also very high.
The reactions of the Co complexes have lower activation barriers than Rh and Ir complexes.
The barriers of the reactions involving olefins with electron-donating groups are generally lower compared to the reactions of the parent (unsubstituted) ethylene while the activation barriers for reactions of olefins with electron-withdrawing groups are generally higher compared to the parent (unsubstituted) ethylene.
The one-step [3 + 2] pathway remains the most favoured irrespective of the metal centre or the nature of the olefin.
The mechanism of the reaction is therefore settled in favour of the [3 + 2] addition pathway.
American Psychological Association (APA)
Opoku, Ernest& Tia, Richard& Adei, Evans. 2016. [3 + 2] versus [2 + 2] Addition: A Density Functional Theory Study on the Mechanistic Aspects of Transition Metal-Assisted Formation of 1,2-Dinitrosoalkanes. Journal of Chemistry،Vol. 2016, no. 2016, pp.1-10.
https://search.emarefa.net/detail/BIM-1107661
Modern Language Association (MLA)
Opoku, Ernest…[et al.]. [3 + 2] versus [2 + 2] Addition: A Density Functional Theory Study on the Mechanistic Aspects of Transition Metal-Assisted Formation of 1,2-Dinitrosoalkanes. Journal of Chemistry No. 2016 (2016), pp.1-10.
https://search.emarefa.net/detail/BIM-1107661
American Medical Association (AMA)
Opoku, Ernest& Tia, Richard& Adei, Evans. [3 + 2] versus [2 + 2] Addition: A Density Functional Theory Study on the Mechanistic Aspects of Transition Metal-Assisted Formation of 1,2-Dinitrosoalkanes. Journal of Chemistry. 2016. Vol. 2016, no. 2016, pp.1-10.
https://search.emarefa.net/detail/BIM-1107661
Data Type
Journal Articles
Language
English
Notes
Includes bibliographical references
Record ID
BIM-1107661