NDLI: Ligand noninnocence in FeNO corroles: insights from β-octabromocorrole complexes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Norheim, Hans-kristian Vazquez-lima, Hugo Einrem, Rune F. Capar, Jan Gagnon, Kevin J. Ghosh, Abhik Beavers, Christine M.
Description	Author Affiliation: Norheim HK ( Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø, Norway. hugo.vazquez@uit.no abhik.ghosh@uit.no.); Capar J ( Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø, Norway. hugo.vazquez@uit.no abhik.ghosh@uit.no.); Einrem RF ( Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø, Norway. hugo.vazquez@uit.no abhik.ghosh@uit.no.); Gagnon KJ ( Advanced Light Source, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA 94720-8229, USA.); Beavers CM ( Advanced Light Source, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA 94720-8229, USA.); Vazquez-Lima H ( Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø, Norway. hugo.vazquez@uit.no abhik.ghosh@uit.no.); Ghosh A ( Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø, Norway. hugo.vazquez@uit.no abhik.ghosh@uit.no.)
Abstract	The first FeNO octabromocorroles have been synthesized including four β-octabromo-meso-tris(p-X-phenyl)corrole derivatives $Fe[Br_{8}TpXPC](NO)$ (X = $CF_{3},$ H, $CH_{3},$ $OCH_{3})$ and the β-octabromo-meso-tris(pentafluorophenyl)corrole complex, $Fe[Br_{8}TPFPC](NO).$ The last complex, which proved amenable to single-crystal X-ray structure determination, exhibits the geometry parameters: Fe–N(O) 1.643(8) Å, N–O 1.158(9) Å, and a FeNO angle of 176.4(6)°. The more electron-deficient complexes exhibit increased instability with respect to NO loss and also higher infrared NO stretching frequencies $(ν_{NO}).$ Interestingly, DFT calculations and IR marker bands indicate a noninnocent $\{FeNO\}^{7}-(corrole˙^{2−})$ formulation for all FeNO corroles, both $β-H_{8}$ and $β-Br_{8},$ with essentially the same degree of corrole radical character. Instead, an electron-deficient corrole appears to exert a field effect resulting in reduced Fe-to-NO backdonation, which accounts for both the increased instability with respect to NO loss and the higher $ν_{NO}`s.$
ISSN	14779226
Issue Number	2
Journal	Dalton Trans.
Volume Number	45
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2016-01-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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