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Nickel complexes have been widely employed as catalysts in C–C and C–heteroatom bond formation reactions. While Ni(0), Ni( i ), and Ni( ii ) intermediates are most relevant in these transformations, recently Ni( iii ) and Ni( iv ) species have also been proposed to play a role in catalysis. Reported herein is the synthesis, detailed characterization, and reactivity of a series of Ni( ii ) and Ni( iii ) metallacycle complexes stabilized by tetradentate pyridinophane ligands with various N-substituents. Interestingly, while the oxidation of the Ni( ii ) complexes with various other oxidants led to exclusive C–C bond formation in very good yields, the use of O 2 or H 2 O 2 as oxidants led to formation of appreciable amounts of C–O bond formation products, especially for the Ni( ii ) complex supported by an asymmetric pyridinophane ligand containing one tosyl N-substituent. Moreover, cryo-ESI-MS studies support the formation of several high-valent Ni species as key intermediates in this uncommon Ni-mediated oxygenase-type chemistry.
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Impact of Oxidation State on Reactivity and Selectivity Differences between Nickel(III) and Nickel(IV) Alkyl Complexes
Abstract Described is a systematic comparison of factors impacting the relative rates and selectivities of C(sp3)−C and C(sp3)−O bond‐forming reactions at high‐valent Ni as a function of oxidation state. Two Ni complexes are compared: a cationic octahedral NiIVcomplex ligated by tris(pyrazolyl)borate and a cationic octahedral NiIIIcomplex ligated by tris(pyrazolyl)methane. Key features of reactivity/selectivity are revealed: 1) C(sp3)−C(sp2) bond‐forming reductive elimination occurs from both centers, but the NiIIIcomplex reacts up to 300‐fold faster than the NiIV, depending on the reaction conditions. The relative reactivity is proposed to derive from ligand dissociation kinetics, which vary as a function of oxidation state and the presence/absence of visible light. 2) Upon the addition of acetate (AcO−), the NiIVcomplex exclusively undergoes C(sp3)−OAc bond formation, while the NiIIIanalogue forms the C(sp3)−C(sp2) coupled product selectively. This difference is rationalized based on the electrophilicity of the respective M−C(sp3) bonds, and thus their relative reactivity towards outer‐sphere SN2‐type bond‐forming reactions.
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- Award ID(s):
- 1664961
- PAR ID:
- 10101567
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 58
- Issue:
- 27
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 9104-9108
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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