Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation

Vincent Porte; Miljan N.M. Milunovic; Ulrich Knof; Thomas Leischner; Tobias Danzl; Daniel Kaiser; Tim Gruene; Michal Zalibera; Ingrid Jelemenska; Lukas Bucinsky; Sergio A.V. Jannuzzi; Serena DeBeer; Ghenadie Novitchi; Nuno Maulide; Vladimir B. Arion

doi:10.1021/jacsau.4c00005

Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation

Vincent Porte
, Miljan N.M. Milunovic
, Ulrich Knof
, Thomas Leischner
, Tobias Danzl
, Daniel Kaiser
, Tim Gruene
, Michal Zalibera
, Ingrid Jelemenska
, Lukas Bucinsky
, Sergio A.V. Jannuzzi
, Serena DeBeer (Korresp. Autor*in)
, Ghenadie Novitchi
, Nuno Maulide (Korresp. Autor*in)
, Vladimir B. Arion (Korresp. Autor*in)

Veröffentlichungen: Beitrag in Fachzeitschrift › Artikel › Peer Reviewed

Abstract

Cobalt complexes with multiproton- and multielectron-responsive ligands are of interest for challenging catalytic transformations. The chemical and redox noninnocence of pentane-2,4-dione bis(S-methylisothiosemicarbazone) (PBIT) in a series of cobalt complexes has been studied by a range of methods, including spectroscopy [UV-vis, NMR, electron paramagnetic resonance (EPR), X-ray absorption spectroscopy (XAS)], cyclic voltammetry, X-ray diffraction, and density functional theory (DFT) calculations. Two complexes [Co^III(H₂L^SMe)I]I and [Co^III(L^SMe)I₂] were found to act as precatalysts in a Wacker-type oxidation of olefins using phenylsilane, the role of which was elucidated through isotopic labeling. Insights into the mechanism of the catalytic transformation as well as the substrate scope of this selective reaction are described, and the essential role of phenylsilane and the noninnocence of PBIT are disclosed. Among the several relevant species characterized was an unprecedented Co(III) complex with a dianionic diradical PBIT ligand ([Co^III(L^SMe••)I]).

Originalsprache	Englisch
Seiten (von - bis)	1166-1183
Seitenumfang	18
Fachzeitschrift	JACS Au
Jahrgang	4
Ausgabenummer	3
Frühes Online-Datum	12 März 2024
DOIs	https://doi.org/10.1021/jacsau.4c00005
Publikationsstatus	Veröffentlicht - 25 März 2024

Fördermittel

V.B.A. and M.N.M.M. are thankful to Austrian Science Fund (FWF) for financial support of this work through Grant No. I4729. V.P., T.L., T.D., D.K., and N.M. acknowledge the European Research Council (ERC CoG 682002) and the University of Vienna for generous funding. S.A.V.J. and S.D. thank the Max Planck Society for funding. Dr. Laure Decamps and Dr. Casey van Stappen are thanked for helping with the beamline experiment. The authors acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III and the authors thank Dr. Wolfgang Caliebe and Dr. Akhil Tayal for assistance in using P64 beamline. Beamtime was allocated for proposal I-20200656. The authors are also indebted to Dr. Hanspeter Ka\u0308hlig for kinetic measurements by NMR spectroscopy and Dr. Agnieszka Nawara-Hultzsch and Mag. Olivera Cvetkovic for the preparation of samples in glovebox. Dr. Adriano Bauer, Dr. Yury Lebedev, and Justin Alich are thanked for preliminary experiments. The authors also thank Dr. Alexander Schnegg for providing access to the EPR facility of MPI CEC. I.J., L.B., and M.Z. acknowledge Projects APVV-19-0024, APVV-20-0213, APVV DS-FR-19-0035, and VEGA (Contract Nos. 1/0139/20, 1/0175/23, and 1/0392/24).

ÖFOS 2012

104015 Organische Chemie
104017 Physikalische Chemie

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10.1021/jacsau.4c00005Lizenz: CC BY 4.0

https://phaidra.univie.ac.at/o:2067287Lizenz: CC BY 4.0

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Zitationsweisen

Porte, V., Milunovic, M. N. M., Knof, U., Leischner, T., Danzl, T., Kaiser, D., Gruene, T., Zalibera, M., Jelemenska, I., Bucinsky, L., Jannuzzi, S. A. V., DeBeer, S., Novitchi, G., Maulide, N., & Arion, V. B. (2024). Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation. JACS Au, 4(3), 1166-1183. https://doi.org/10.1021/jacsau.4c00005

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title = "Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation",

abstract = "Cobalt complexes with multiproton- and multielectron-responsive ligands are of interest for challenging catalytic transformations. The chemical and redox noninnocence of pentane-2,4-dione bis(S-methylisothiosemicarbazone) (PBIT) in a series of cobalt complexes has been studied by a range of methods, including spectroscopy [UV-vis, NMR, electron paramagnetic resonance (EPR), X-ray absorption spectroscopy (XAS)], cyclic voltammetry, X-ray diffraction, and density functional theory (DFT) calculations. Two complexes [CoIII(H2LSMe)I]I and [CoIII(LSMe)I2] were found to act as precatalysts in a Wacker-type oxidation of olefins using phenylsilane, the role of which was elucidated through isotopic labeling. Insights into the mechanism of the catalytic transformation as well as the substrate scope of this selective reaction are described, and the essential role of phenylsilane and the noninnocence of PBIT are disclosed. Among the several relevant species characterized was an unprecedented Co(III) complex with a dianionic diradical PBIT ligand ([CoIII(LSMe••)I]).",

keywords = "cobalt, ketone, multiproton, noninnocence, olefin, oxidation, pentane-2,4-dione bis(S-methylisothiosemicarbazone), redox",

author = "Vincent Porte and Milunovic, \{Miljan N.M.\} and Ulrich Knof and Thomas Leischner and Tobias Danzl and Daniel Kaiser and Tim Gruene and Michal Zalibera and Ingrid Jelemenska and Lukas Bucinsky and Jannuzzi, \{Sergio A.V.\} and Serena DeBeer and Ghenadie Novitchi and Nuno Maulide and Arion, \{Vladimir B.\}",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society.",

year = "2024",

month = mar,

day = "25",

doi = "10.1021/jacsau.4c00005",

language = "English",

volume = "4",

pages = "1166--1183",

journal = "JACS Au",

issn = "2691-3704",

publisher = "ACS Publications",

number = "3",

}

Porte, V, Milunovic, MNM, Knof, U, Leischner, T, Danzl, T, Kaiser, D , Gruene, T, Zalibera, M, Jelemenska, I, Bucinsky, L, Jannuzzi, SAV, DeBeer, S, Novitchi, G, Maulide, N & Arion, VB 2024, 'Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation', JACS Au, Jg. 4, Nr. 3, S. 1166-1183. https://doi.org/10.1021/jacsau.4c00005

TY - JOUR

T1 - Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation

AU - Porte, Vincent

AU - Milunovic, Miljan N.M.

AU - Knof, Ulrich

AU - Leischner, Thomas

AU - Danzl, Tobias

AU - Kaiser, Daniel

AU - Gruene, Tim

AU - Zalibera, Michal

AU - Jelemenska, Ingrid

AU - Bucinsky, Lukas

AU - Jannuzzi, Sergio A.V.

AU - DeBeer, Serena

AU - Novitchi, Ghenadie

AU - Maulide, Nuno

AU - Arion, Vladimir B.

PY - 2024/3/25

Y1 - 2024/3/25

N2 - Cobalt complexes with multiproton- and multielectron-responsive ligands are of interest for challenging catalytic transformations. The chemical and redox noninnocence of pentane-2,4-dione bis(S-methylisothiosemicarbazone) (PBIT) in a series of cobalt complexes has been studied by a range of methods, including spectroscopy [UV-vis, NMR, electron paramagnetic resonance (EPR), X-ray absorption spectroscopy (XAS)], cyclic voltammetry, X-ray diffraction, and density functional theory (DFT) calculations. Two complexes [CoIII(H2LSMe)I]I and [CoIII(LSMe)I2] were found to act as precatalysts in a Wacker-type oxidation of olefins using phenylsilane, the role of which was elucidated through isotopic labeling. Insights into the mechanism of the catalytic transformation as well as the substrate scope of this selective reaction are described, and the essential role of phenylsilane and the noninnocence of PBIT are disclosed. Among the several relevant species characterized was an unprecedented Co(III) complex with a dianionic diradical PBIT ligand ([CoIII(LSMe••)I]).

AB - Cobalt complexes with multiproton- and multielectron-responsive ligands are of interest for challenging catalytic transformations. The chemical and redox noninnocence of pentane-2,4-dione bis(S-methylisothiosemicarbazone) (PBIT) in a series of cobalt complexes has been studied by a range of methods, including spectroscopy [UV-vis, NMR, electron paramagnetic resonance (EPR), X-ray absorption spectroscopy (XAS)], cyclic voltammetry, X-ray diffraction, and density functional theory (DFT) calculations. Two complexes [CoIII(H2LSMe)I]I and [CoIII(LSMe)I2] were found to act as precatalysts in a Wacker-type oxidation of olefins using phenylsilane, the role of which was elucidated through isotopic labeling. Insights into the mechanism of the catalytic transformation as well as the substrate scope of this selective reaction are described, and the essential role of phenylsilane and the noninnocence of PBIT are disclosed. Among the several relevant species characterized was an unprecedented Co(III) complex with a dianionic diradical PBIT ligand ([CoIII(LSMe••)I]).

KW - cobalt

KW - ketone

KW - multiproton

KW - noninnocence

KW - olefin

KW - oxidation

KW - pentane-2,4-dione bis(S-methylisothiosemicarbazone)

KW - redox

UR - https://www.scopus.com/pages/publications/85187683070

U2 - 10.1021/jacsau.4c00005

DO - 10.1021/jacsau.4c00005

M3 - Article

AN - SCOPUS:85187683070

SN - 2691-3704

VL - 4

SP - 1166

EP - 1183

JO - JACS Au

JF - JACS Au

IS - 3

ER -

Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation

Abstract

Fördermittel

ÖFOS 2012

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