Selective Oxidation of C-H Bonds through a Manganese(III) Hydroperoxo in MnII-Exchanged CFA-1

Amanda W Stubbs; Mircea Dincǎ

doi:10.1021/acs.inorgchem.9b02068

Selective Oxidation of C-H Bonds through a Manganese(III) Hydroperoxo in Mn^II-Exchanged CFA-1

Inorg Chem. 2019 Oct 7;58(19):13221-13228. doi: 10.1021/acs.inorgchem.9b02068. Epub 2019 Sep 25.

Authors

Amanda W Stubbs¹, Mircea Dincǎ¹

Affiliation

¹ Department of Chemistry , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , Massachusetts 02139 , United States.

PMID: 31553170
DOI: 10.1021/acs.inorgchem.9b02068

Abstract

Partial substitution of Zn^II by Mn^II in Zn₅(OAc)₄(5,5'-bibenzo[d][1,2,3]triazole)₃ (CFA-1) results in a Mn^II species supported by three nitrogen ligands and a charge-balancing anion, a structure reminiscent of those found in molecular "scorpionate" complexes. Unlike molecular manganese(II) scorpionates, Mn-CFA-1 is capable of catalytically activating oxygen from air to oxidize C-H bonds up to 87 kcal/mol in strength. A series of in situ spectroscopic studies, including diffuse-reflectance UV-vis, diffuse-reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy, reveal that catalysis likely proceeds through a manganese(III) hydroperoxo that is only accessed in the presence of a hydrogen-atom donor. These results demonstrate that the site isolation provided in metal-organic frameworks enables the generation and utilization of highly reactive species for catalysis that are inaccessible in molecular systems.