Organometallic chemistry of new carbon materials. Structure and dynamic behavior of group 6 metal tricabonyl complexes of graphene and perforated graphene: a DFT study

The mechanism of inter-ring haptotropic rearrangements (IRHRs) was investigated by DFT for the tricarbonyl η 6 -complexes of group 6 metals (M = Cr, Mo, W) of coronene ( I-M ), kekulene ( II-M ) and a model graphene ( III-M ). The computed η 6 ,η 6 -IRHR activation barriers in the middle size PAHs I...

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Bibliographic Details
Published in:New journal of chemistry 2019, Vol.43 (46), p.17991-182
Main Authors: Zhulyaev, N. S, Gloriozov, I. P, Nechaev, M. S, Gam, F, Oprunenko, Yu. F, Saillard, J.-Y
Format: Article
Language:English
Subjects:
Chemical Sciences
Coordination chemistry
Coordination compounds
Graphene
Molybdenum
Naphthalene
or physical chemistry
Organic chemistry
Organometallic compounds
Theoretical and
Tricarbonylchromium
Tungsten
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Summary:The mechanism of inter-ring haptotropic rearrangements (IRHRs) was investigated by DFT for the tricarbonyl η 6 -complexes of group 6 metals (M = Cr, Mo, W) of coronene ( I-M ), kekulene ( II-M ) and a model graphene ( III-M ). The computed η 6 ,η 6 -IRHR activation barriers in the middle size PAHs I-M and II-M were calculated to be substantially lower than those in the case of complexes of relatively small size PAHs such as naphthalene chromium tricarbonyl (Δ G # 20-25 kcal mol −1 vs. 30 kcal mol −1 ). The barrier is further lowered in the case of the model graphene complex III-Cr (Δ G # 13 kcal mol −1 ). An even lower barrier is found for III-Mo (Δ G # 10 kcal mol −1 ), whereas it slightly increases for III-W (Δ G # 14 kcal mol −1 ). Low energy barriers are found for inter-ring haptotropic rearrangements on large PAH ligands.
ISSN:1144-0546
1369-9261
DOI:10.1039/c9nj02187f