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Electronic Structures of Nickel(II)-Bis(indanyloxazoline)-dihalide Catalysts: Understanding Ligand Field Contributions That Promote C(sp(2))-C(sp(3)) Cross-Coupling
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SYSNO ASEP 0575712 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Electronic Structures of Nickel(II)-Bis(indanyloxazoline)-dihalide Catalysts: Understanding Ligand Field Contributions That Promote C(sp(2))-C(sp(3)) Cross-Coupling Author(s) McNicholas, B. J. (US)
Tong, Z. J. (US)
Bím, D. (US)
Turro, R. F. (US)
Kazmierczak, N. P. (US)
Chalupský, Jakub (UFCH-W) ORCID, RID
Reisman, S. E. (US)
Hadt, R. G. (US)Source Title Inorganic Chemistry. - : American Chemical Society - ISSN 0020-1669
Roč. 62, č. 34 (2023), s. 14010-14027Number of pages 18 s. Language eng - English Country US - United States Keywords TETRAHEDRAL NICKEL(II) COMPLEXES ; MAGNETIC CIRCULAR-DICHROISM ; FUNCTIONAL THEORY APPROACH Subject RIV CF - Physical ; Theoretical Chemistry OECD category Physical chemistry Method of publishing Limited access Institutional support UFCH-W - RVO:61388955 UT WOS 001049425000001 EID SCOPUS 85168799063 DOI 10.1021/acs.inorgchem.3c02048 Annotation NiII(IB) dihalide [IB = (3aR,3a′R,8aS,8a′S)-2,2′-(cyclopropane-1,1-diyl)bis(3a,8a-dihydro-8H-indeno[1,2-d]-oxazole)] complexes are representative of a growing class of first-row transition-metal catalysts for the enantioselective reductive cross-coupling of C(sp2) and C(sp3) electrophiles. Recent mechanistic studies highlight the complexity of these ground-state cross-couplings but also illuminate new reactivity pathways stemming from one-electron redox and their significant sensitivities to reaction conditions. For the first time, a diverse array of spectroscopic methods coupled to electrochemistry have been applied to NiII-based precatalysts to evaluate specific ligand field effects governing key Ni-based redox potentials. We also experimentally demonstrate DMA solvent coordination to catalytically relevant Ni complexes. Coordination is shown to favorably influence key redox-based reaction steps and prevent other deleterious Ni-based equilibria. Combined with electronic structure calculations, we further provide a direct correlation between reaction intermediate frontier molecular orbital energies and cross-coupling yields. Considerations developed herein demonstrate the use of synergic spectroscopic and electrochemical methods to provide concepts for catalyst ligand design and rationalization of reaction condition optimization. © 2023 American Chemical Society. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2024 Electronic address https://hdl.handle.net/11104/0345453
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