Structural and Spectroscopic Evidence for a Side-on Fe(III)–Superoxo Complex Featuring Discrete O–O Bond Distances

Autor:	Zong-Han Wu, Gene-Hsiang Lee, Pu Ge, Hung-Ruei Pan, Hsin-Jou Chen, Hua Fen Hsu, Shengfa Ye
Jazyk:	angličtina
Rok vydání:	2021
Předmět:	superoxo Valence (chemistry) Coordination sphere Chemistry Intermolecular force Electronic structure Article Bond length Crystallography non-heme iron Ab initio quantum chemistry methods O2 ligand intermediate Potential energy surface iron−superoxo complex Density functional theory QD1-999
Zdroj:	JACS Au, Vol 1, Iss 9, Pp 1389-1398 (2021) JACS Au
ISSN:	2691-3704
Popis:	The O–O bond length is often used as a structural indicator to determine the valence states of bound O2 ligands in biological metal–dioxygen intermediates and related biomimetic complexes. Here, we report very distinct O–O bond lengths found for three crystallographic forms (1.229(4), 1.330(4), 1.387(2) Å at 100 K) of a side-on iron–dioxygen species. Despite their different O–O bond distances, all forms possess the same electronic structure of Fe(III)–O2•–, as evidenced by their indistinguishable spectroscopic features. Density functional theory and ab initio calculations, which successfully reproduce spectroscopic parameters, predict a flat potential energy surface of an η2-O2 motif binding to the iron center regarding the O–O distance. Therefore, the discrete O–O bond lengths observed likely arise from differential intermolecular interactions in the second coordination sphere. The work suggests that the O–O distance is not a reliable benchmark to unequivocally identify the valence state of O2 ligands for metal–dioxygen species in O2-utilizing metalloproteins and synthetic complexes.
Databáze:	OpenAIRE
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