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One pot synthesis of two cobalt(iii) Schiff base complexes with chelating pyridyltetrazolate and exploration of their bio-relevant catalytic activities.

ABSTRACT: Two new cobalt(iii) tetrazolato complexes [Co(L¹)(PTZ)(N₃)] (1) and [Co(L²)(PTZ)(N₃)] (2) {where H₂L¹ = 2((3-(methylamino)propylimino)methyl)-6-methoxyphenol, H₂L² = 2((3-(dimethylamino)propylimino)methyl)-6-ethoxyphenol and HPTZ = 5-(2-pyridyl)tetrazole}, have been synthesized via in situ 1,3-dipolar cycloaddition reaction of 2-cyanopyridine and sodium azide in the presence of cobalt(ii) nitrate hexahydrate and respective Schiff bases in the open atmosphere. The structures of both complexes have been confirmed by single crystal X-ray diffraction studies. Features of noncovalent interactions in the solid state of both complexes have been studied by means of DFT and MEP calculations and characterized using Bader's theory of "atoms in molecules" (AIM). These complexes act as biomimetic catalysts promoting the aerobic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to the corresponding o-benzoquinone at room temperature. The reaction follows Michaelis-Menten enzymatic reaction kinetics with turnover numbers of ∼0.030 s^-1 in an acetonitrile-methanol (2 : 1) mixture. Both complexes are also reactive towards aerobic oxidation of o-aminophenol in acetonitrile-methanol (2 : 1) with turnover numbers ∼0.095 s^-1.

SUBMITTER: Ghosh K

PROVIDER: S-EPMC9084250 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

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One pot synthesis of two cobalt(iii) Schiff base complexes with chelating pyridyltetrazolate and exploration of their bio-relevant catalytic activities.

Ghosh Kousik K Banerjee Abhisek A Bauzá Antonio A Frontera Antonio A Chattopadhyay Shouvik S

RSC advances 20180807 49

Two new cobalt(iii) tetrazolato complexes [Co(L1)(PTZ)(N3)] (1) and [Co(L2)(PTZ)(N3)] (2) {where H2L1 = 2((3-(methylamino)propylimino)methyl)-6-methoxyphenol, H2L2 = 2((3-(dimethylamino)propylimino)methyl)-6-ethoxyphenol and HPTZ = 5-(2-pyridyl)tetrazole}, have been synthesized via in situ 1,3-dipolar cycloaddition reaction of 2-cyanopyridine and sodium azide in the presence of cobalt(ii) nitrate hexah ...[more]

PMID: 35542722

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Project description:The reaction of 2,6-diformyl-4-methylphenol (DFMF) with 1-amino-2-propanol (AP) and tris(hydroxymethyl)aminomethane (THMAM) was investigated in the presence of Cobalt(II) salts, (X = ClO4-, CH3CO2-, Cl-, NO3-), sodium azide (NaN3), and triethylamine (TEA). In one pot, the variation in Cobalt(II) salt results in the self-assembly of dinuclear, tetranuclear, and H-bonding-directed polynuclear coordination complexes of Cobalt(III), Cobalt(II), and mixed-valence CoIICoIII: [Co2III(H2L-1)2(AP-1)(N3)](ClO4)2 (1), [Co4(H2L-1)2(µ3-1,1,1-N3)2(µ-1,1-N3)2Cl2(CH3OH)2]·4CH3OH (2), [Co2IICo2III(HL-2)2(µ-CH3CO2)2(µ3-OH)2](NO3)2·2CH3CH2OH (3), and [Co2IICo2III (H2L12-)2(THMAM-1)2](NO3)4 (4). In 1, two cobalt(III) ions are connected via three single atom bridges; two from deprotonated ethanolic oxygen atoms in the side arms of the ligands and one from the1-amino-2-propanol moiety forming a dinuclear unit with a very short (2.5430(11) Å) Co-Co intermetallic separation with a coordination number of 7, a rare feature for cobalt(III). In 2, two cobalt(II) ions in a dinuclear unit are bridged through phenoxide O and μ3-1,1,1-N3 azido bridges, and the two dinuclear units are interconnected by two μ-1,1-N3 and two μ3-1,1,1-N3 azido bridges generating tetranuclear cationic [Co4(H2L-1)2(µ3-1,1,1-N3)2(µ-1,1-N3)2Cl2(CH3OH)2]2+ units with an incomplete double cubane core, which grow into polynuclear 1D-single chains along the a-axis through H-bonding. In 3, HL2- holds mixed-valent Co(II)/Co(III) ions in a dinuclear unit bridged via phenoxide O, μ-1,3-CH3CO2-, and μ3-OH- bridges, and the dinuclear units are interconnected through two deprotonated ethanolic O in the side arms of the ligands and two μ3-OH- bridges generating cationic tetranuclear [Co2IICo2III(HL-2)2(µ-CH3CO2)2(µ3-OH)2]2+ units with an incomplete double cubane core. In 4, H2L1-2 holds mixed-valent Co(II)/Co(III) ions in dinuclear units which dimerize through two ethanolic O (μ-RO-) in the side arms of the ligands and two ethanolic O (μ3-RO-) of THMAM bridges producing centrosymmetric cationic tetranuclear [Co2IICo2III (H2L1-2)2(THMAM-1)2]4+ units which grow into 2D-sheets along the bc-axis through a network of H-bonding. Bulk magnetization measurements on 2 demonstrate that the magnetic interactions are completely dominated by an overall ferromagnetic coupling occurring between Co(II) ions.

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Dataset Information

One pot synthesis of two cobalt(iii) Schiff base complexes with chelating pyridyltetrazolate and exploration of their bio-relevant catalytic activities.

Publications

One pot synthesis of two cobalt(iii) Schiff base complexes with chelating pyridyltetrazolate and exploration of their bio-relevant catalytic activities.

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