TY - JOUR
T1 - Synthesis, Characterization, and Efficient Catalytic Activities of a Nickel(II) Porphyrin
T2 - Remarkable Solvent and Substrate Effects on Participation of Multiple Active Oxidants
AU - Ahn, Hye Mi
AU - Bae, Jeong Mi
AU - Kim, Min Jeong
AU - Bok, Kwon Hee
AU - Jeong, Ha Young
AU - Lee, Suk Joong
AU - Kim, Cheal
N1 - Funding Information:
Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2014R1A2A1A11051794 and NRF-2016M3D3A1A01913239 for the Korea C1 Gas Refinery R&D Center) are gratefully acknowledged.
Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/9/4
Y1 - 2017/9/4
N2 - A new nickel(II) porphyrin complex, [NiII(porp)] (1), has been synthesized and characterized by 1H NMR, 13C NMR and mass spectrometry analysis. This NiII porphyrin complex 1 quantitatively catalyzed the epoxidation reaction of a wide range of olefins with meta-chloroperoxybenzoic acid (m-CPBA) under mild conditions. Reactivity and Hammett studies, H2 18O-exchange experiments, and the use of PPAA (peroxyphenylacetic acid) as a mechanistic probe suggested that participation of multiple active oxidants NiII−OOC(O)R 2, NiIV-Oxo 3, and NiIII-Oxo 4 within olefin epoxidation reactions by the nickel porphyrin complex is markedly affected by solvent polarity, concentration, and type of substrate. In aprotic solvent systems, such as toluene, CH2Cl2, and CH3CN, multiple oxidants, NiII−(O)R 2, NiIV-Oxo 3, and NiIII-Oxo 4, operate simultaneously as the key active intermediates responsible for epoxidation reactions of easy-to-oxidize substrate cyclohexene, whereas NiIV-Oxo 3 and NiIII-Oxo 4 species become the common reactive oxidant for the difficult-to-oxidize substrate 1-octene. In a protic solvent system, a mixture of CH3CN and H2O (95:5), the NiII−OOC(O)R 2 undergoes heterolytic or homolytic O−O bond cleavage to afford NiIV-Oxo 3 and NiIII-Oxo 4 species by general acid catalysis prior to direct interaction between 2 and olefin, regardless of the type of substrate. In this case, only NiIV-Oxo 3 and NiIII-Oxo 4 species were the common reactive oxidant responsible for olefin epoxidation reactions.
AB - A new nickel(II) porphyrin complex, [NiII(porp)] (1), has been synthesized and characterized by 1H NMR, 13C NMR and mass spectrometry analysis. This NiII porphyrin complex 1 quantitatively catalyzed the epoxidation reaction of a wide range of olefins with meta-chloroperoxybenzoic acid (m-CPBA) under mild conditions. Reactivity and Hammett studies, H2 18O-exchange experiments, and the use of PPAA (peroxyphenylacetic acid) as a mechanistic probe suggested that participation of multiple active oxidants NiII−OOC(O)R 2, NiIV-Oxo 3, and NiIII-Oxo 4 within olefin epoxidation reactions by the nickel porphyrin complex is markedly affected by solvent polarity, concentration, and type of substrate. In aprotic solvent systems, such as toluene, CH2Cl2, and CH3CN, multiple oxidants, NiII−(O)R 2, NiIV-Oxo 3, and NiIII-Oxo 4, operate simultaneously as the key active intermediates responsible for epoxidation reactions of easy-to-oxidize substrate cyclohexene, whereas NiIV-Oxo 3 and NiIII-Oxo 4 species become the common reactive oxidant for the difficult-to-oxidize substrate 1-octene. In a protic solvent system, a mixture of CH3CN and H2O (95:5), the NiII−OOC(O)R 2 undergoes heterolytic or homolytic O−O bond cleavage to afford NiIV-Oxo 3 and NiIII-Oxo 4 species by general acid catalysis prior to direct interaction between 2 and olefin, regardless of the type of substrate. In this case, only NiIV-Oxo 3 and NiIII-Oxo 4 species were the common reactive oxidant responsible for olefin epoxidation reactions.
KW - multiple active oxidants
KW - ni-oxo species
KW - nickel
KW - olefin epoxidation
KW - porphyrins
UR - http://www.scopus.com/inward/record.url?scp=85028612647&partnerID=8YFLogxK
U2 - 10.1002/chem.201702750
DO - 10.1002/chem.201702750
M3 - Article
C2 - 28731593
AN - SCOPUS:85028612647
SN - 0947-6539
VL - 23
SP - 11969
EP - 11976
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 49
ER -