TY - JOUR

T1 - Reactivity vs. Selectivity of Biomimetic Catalyst Systems of the Fe(PDP) Family through the Nature and Spin State of the Active Iron-Oxygen Species

AU - Zima, Alexandra M.

AU - Lyakin, Oleg Y.

AU - Bryliakova, Anna A.

AU - Babushkin, Dmitrii E.

AU - Bryliakov, Konstantin P.

AU - Talsi, Evgenii P.

N1 - Funding Information: The authors acknowledge funding from the Ministry of Science and Higher Education within the governmental orders for Boreskov Institute of Catalysis (project AAAA‐A21‐121011390008‐4). AAB acknowledges the access to the supercomputer facilities of the Computing Centre of Novosibirsk State University. Publisher Copyright: © 2022 The Chemical Society of Japan & Wiley-VCH GmbH

PY - 2022/5

Y1 - 2022/5

N2 - Catalytic approaches to late-stage creation of new C−O bonds, especially via oxygenation of particular C−H groups in complex organic molecules, provide challenging tools for the synthesis of biologically active compounds and candidate drugs. In the last decade, significant efforts were invested in designing bioinspired iron based catalyst systems, capable of conducting selective oxidations of organic compounds. The key role of the oxygen-transferring high-valent iron-oxygen species in selective oxygenation is now well established; the next logical step would be gaining insight into the factors governing the oxidation chemo- and stereoselectivity, in relation to the peculiarities of their electronic structure, which would allow introducing the desired level of predictability into those catalytic transformations. In this Personal Account we analyze recent data on the reactivity of bioinspired formally oxoiron(V) catalytically active sites toward organic substrates having C=C and C(sp3)−H groups. While the majority of reported oxoiron(V) active species are low-spin (S=1/2) complexes, the presence of strong electron-donating groups (NR1R2) in the ligand backbone favors the high-spin (S=3/2) ground state. Remarkably, the high-spin perferryl species exhibit higher chemo-, regio-, and stereoselectivity in the oxidations than their low-spin counterparts, thus witnessing the significance of these subtle electronic effects for the selectivity of oxidations conducted by bioinspired catalysts of the Fe(PDP) family.

AB - Catalytic approaches to late-stage creation of new C−O bonds, especially via oxygenation of particular C−H groups in complex organic molecules, provide challenging tools for the synthesis of biologically active compounds and candidate drugs. In the last decade, significant efforts were invested in designing bioinspired iron based catalyst systems, capable of conducting selective oxidations of organic compounds. The key role of the oxygen-transferring high-valent iron-oxygen species in selective oxygenation is now well established; the next logical step would be gaining insight into the factors governing the oxidation chemo- and stereoselectivity, in relation to the peculiarities of their electronic structure, which would allow introducing the desired level of predictability into those catalytic transformations. In this Personal Account we analyze recent data on the reactivity of bioinspired formally oxoiron(V) catalytically active sites toward organic substrates having C=C and C(sp3)−H groups. While the majority of reported oxoiron(V) active species are low-spin (S=1/2) complexes, the presence of strong electron-donating groups (NR1R2) in the ligand backbone favors the high-spin (S=3/2) ground state. Remarkably, the high-spin perferryl species exhibit higher chemo-, regio-, and stereoselectivity in the oxidations than their low-spin counterparts, thus witnessing the significance of these subtle electronic effects for the selectivity of oxidations conducted by bioinspired catalysts of the Fe(PDP) family.

KW - C−H activation

KW - homogeneous catalysis

KW - iron

KW - reaction mechanism

KW - selective oxidation

KW - Oxygen/chemistry

KW - Reactive Oxygen Species

KW - Biomimetics

KW - Oxidation-Reduction

KW - Catalysis

KW - Iron/chemistry

UR - http://www.scopus.com/inward/record.url?scp=85124754254&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/182ef6a3-be1b-319a-bfc7-76c5d78a8a61/

U2 - 10.1002/tcr.202100334

DO - 10.1002/tcr.202100334

M3 - Review article

C2 - 35142426

AN - SCOPUS:85124754254

VL - 22

JO - Chemical Record

JF - Chemical Record

SN - 1527-8999

IS - 5

M1 - e202100334

ER -