NDLI: DFT study of intramolecular interring $η^{6},η^{6}-haptotropic$ rearrangements in tricarbonylchromium complexes of 2-aminobiphenyl and 4-aminobiphenyl

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Fetisov, Evgenii O. Czerwinski, Curtis J. Gloriozov, Igor P. Oprunenko, Yuri F.
Description	Author Affiliation: Czerwinski CJ ( Department of Chemistry, University of Wisconsin-La Crosse, 1725 State Street, La Crosse, WI 54601, USA. cczerwinski@uwlax.edu)
Abstract	DFT studies have been carried out to investigate the role of nitrogen participation in the interring haptotropic rearrangements of $[(η^{6}-C_{6}H_{5})(C_{6}H_{4}-4-NH_{2})]Cr(CO)_{3}$ and $[(η^{6}-C_{6}H_{5})(C_{6}H_{4}-2-NH_{2})]Cr(CO)_{3}.$ For the para-substituted case, where intramolecular coordination of nitrogen to chromium is not possible, DFT modeling predicts an activation barrier of 32.5 kcal $mol^{−1},$ which is in very close agreement with the experimentally determined value of 32.57 kcal $mol^{−1}.$ In the case of the ortho-substituted isomers, modeling of a mechanism that does not invoke stabilization via nitrogen coordination yields a predicted energy barrier of 32.7 kcal $mol^{−1},$ while a mechanism that does invoke nitrogen participation and accounts for interconversion of rotational isomers gives a predicted value of 30.2 kcal $mol^{−1}.$ This is consistent with the experimentally determined value of 31.22 kcal $mol^{−1}.$ These data provide evidence that intramolecular stabilization via nitrogen coordination to chromium is responsible for the ortho substituted isomer undergoing haptotropic rearrangement with a rate nearly five times greater than that observed for the para isomer. For the mechanism that invokes ortho-amino group participation, transition state analysis in the frame of Bader theory shows that each transition state along the proposed mechanistic pathway has a bond critical point between nitrogen and chromium.
ISSN	14779226
Issue Number	29
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-08-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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