Aerobic C-C and C-O bond formation reactions mediated by high-valent nickel species

Sofia M. Smith, Oriol Planas, Laura Gómez, Nigam P. Rath, Xavi Ribas, Liviu M. Mirica

Research output: Contribution to journalArticle

Abstract

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 O2 or H2O2 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.

Original languageEnglish (US)
Pages (from-to)10366-10372
Number of pages7
JournalChemical Science
Volume10
Issue number44
DOIs
StatePublished - Jan 1 2019

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Nickel
Oxidants
Ligands
Oxygenases
Catalysis
Oxidation
Catalysts

ASJC Scopus subject areas

  • Chemistry(all)

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Aerobic C-C and C-O bond formation reactions mediated by high-valent nickel species. / Smith, Sofia M.; Planas, Oriol; Gómez, Laura; Rath, Nigam P.; Ribas, Xavi; Mirica, Liviu M.

In: Chemical Science, Vol. 10, No. 44, 01.01.2019, p. 10366-10372.

Research output: Contribution to journalArticle

Smith, SM, Planas, O, Gómez, L, Rath, NP, Ribas, X & Mirica, LM 2019, 'Aerobic C-C and C-O bond formation reactions mediated by high-valent nickel species', Chemical Science, vol. 10, no. 44, pp. 10366-10372. https://doi.org/10.1039/c9sc03758f
Smith, Sofia M. ; Planas, Oriol ; Gómez, Laura ; Rath, Nigam P. ; Ribas, Xavi ; Mirica, Liviu M. / Aerobic C-C and C-O bond formation reactions mediated by high-valent nickel species. In: Chemical Science. 2019 ; Vol. 10, No. 44. pp. 10366-10372.
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