Substrate-dependent aromatic ring fission of catechol and 2-aminophenol with O2 catalyzed by a nonheme iron complex of a tripodal N4 ligand.

Content Provider	Semantic Scholar
Author	Lakshman, Triloke Ranjan Chatterjee, Sayanti Chakraborty, Biswarup Paine, Tapan Kanti
Copyright Year	2016
Abstract	The catalytic reactivity of an iron(ii) complex [(TPA)Fe(II)(CH3CN)2](2+) (1) (TPA = tris(2-pyridylmethyl)amine) towards oxygenative aromatic C-C bond cleavage of catechol and 2-aminophenol is presented. Complex 1 exhibits catalytic and regioselective C-C bond cleavage of 3,5-di-tert-butylcatechol (H2DBC) to form intradiol products, whereas it catalyzes extradiol-type C-C bond cleavage of 2-amino-4,6-di-tert-butylphenol (H2AP). The catalytic reactions are found to be pH-dependent and the complex exhibits maximum turnovers at pH 5 in acetonitrile-phthalate buffer. An iron(iii)-catecholate complex [(TPA)Fe(III)(DBC)](+) (2) is formed in the ring cleavage of catechol. In the extradiol-type cleavage of H2AP, an iron(iii)-2-iminobenzosemiquinonate complex [(TPA)Fe(III)(ISQ)](2+) (3) (ISQ = 4,6-di-tert-butyl-2-iminobenzosemiquinonate radical anion) is observed in the reaction pathway. This work shows the importance of the nature of 'redox non-innocent' substrates in governing the mode of ring fission reactivity.
File Format	PDF HTM / HTML
DOI	10.1039/c5dt04541j
PubMed reference number	27148606
Journal	Medline
Volume Number	45
Issue Number	21
Alternate Webpage(s)	http://www.rsc.org/suppdata/c5/dt/c5dt04541j/c5dt04541j1.pdf
Alternate Webpage(s)	https://doi.org/10.1039/c5dt04541j
Journal	Dalton transactions
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article