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Title: Cu(i) complexes obtained: Via spontaneous reduction of Cu(ii) complexes supported by designed bidentate ligands: Bioinspired Cu(i) based catalysts for aromatic hydroxylation
Authors: Kumari S.
Muthuramalingam S.
Dhara A.K.
Singh, Udai Pratap
Mayilmurugan R.
Ghosh, Kaushik
Published in: Dalton Transactions
Abstract: Copper(i) complexes [Cu(L1-7)2](ClO4) (1-7) of bidentate ligands (L1-L7) have been synthesized via spontaneous reduction and characterized as catalysts for aromatic C-H activation using H2O2 as the oxidant. The single crystal X-ray structure of 1 exhibited a distorted tetrahedral geometry. All the copper(i) complexes catalyzed direct hydroxylation of benzene to form phenol with good selectivity up to 98%. The determined kinetic isotope effect (KIE) values, 1.69-1.71, support the involvement of a radical type mechanism. The isotope-labeling experiments using H218O2 showed 92% incorporation of 18O into phenol and confirm that H2O2 is the key oxygen supplier. Overall, the catalytic efficiencies of the complexes are strongly influenced by the electronic and steric factor of the ligand, which is fine-tuned by the ligand architecture. The benzene hydroxylation reaction possibly proceeded via a radical mechanism, which was confirmed by the addition of radical scavengers (TEMPO) to the catalytic reaction that showed a reduction in phenol formation.
Citation: Dalton Transactions(2020), 49(39): 13829-13839
Issue Date: 2020
Publisher: Royal Society of Chemistry
Keywords: Activation analysis
Crystal structure
Single crystals
Synthesis (chemical)
Aromatic hydroxylation
Benzene hydroxylation
Catalytic efficiencies
Copper (i) comple
ISSN: 14779226
Author Scopus IDs: 57209199241
Author Affiliations: Kumari, S., Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India
Muthuramalingam, S., Bioinorganic Chemistry Laboratory/Physical Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai, 625021, India
Funding Details: Ministry of Human Resource Development, MHRD Science and Engineering Research Board, SERB University Grants Committee, UGC Bangladesh Council of Scientific and Industrial Research, BCSIR: 09/114(0224)/19-EMRI.KG is thankful to CSIR, New Delhi, India, for financial assistance (No. 01(2942)/18/EMR-II dated 01-05-2018). SK is thankful to CSIR, AKD is thankful to UGC and AM is thankful to MHRD, India, for financial assistance. RM acknowledges the Science and Engin
Corresponding Author: Ghosh, K.; Department of Chemistry, India; email: Mayilmurugan, R.; Bioinorganic Chemistry Laboratory/Physical Chemistry, India; email:
Appears in Collections:Journal Publications [CY]

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