Počet záznamů: 1
Electronic Structures of Nickel(II)-Bis(indanyloxazoline)-dihalide Catalysts: Understanding Ligand Field Contributions That Promote C(sp(2))-C(sp(3)) Cross-Coupling
- 1.0575375 - ÚOCHB 2024 RIV US eng J - Článek v odborném periodiku
McNicholas, B. J. - Tong, Z. J. - Bím, D. - Turro, R. F. - Kazmierczak, N. P. - Chalupský, Jakub - Reisman, S. E. - Hadt, R. G.
Electronic Structures of Nickel(II)-Bis(indanyloxazoline)-dihalide Catalysts: Understanding Ligand Field Contributions That Promote C(sp(2))-C(sp(3)) Cross-Coupling.
Inorganic Chemistry. Roč. 62, č. 34 (2023), s. 14010-14027. ISSN 0020-1669. E-ISSN 1520-510X
Grant CEP: GA ČR(CZ) GJ20-06451Y
GRANT EU: European Commission(XE) 883987 - PhotoRedOx
Institucionální podpora: RVO:61388963
Klíčová slova: tetrahedral nickel(II) complexes * magnetic circular dichroism * functional theory approach
Obor OECD: Physical chemistry
Impakt faktor: 4.6, rok: 2022
Způsob publikování: Omezený přístup
https://doi.org/10.1021/acs.inorgchem.3c02048
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.
Trvalý link: https://hdl.handle.net/11104/0345170
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