title: Competitive coordination aggregation for V-shaped [Co3] and disc-like [Co7] complexes: synthesis, magnetic properties and catechol oxidase activity.
abstract: Unique dependence on the nature of metal salt and reaction conditions for coordination assembly reactions of varying architecture and nuclearity have been identified in V-shaped [Co3L4] and planar disc-like [Co7L6] compounds: [CoL2(μ-L)2(μ-OH2)2(CF3CO2)2] (1) and [Co(μ-L)6(μ-OMe)6]Cl2 (2) (HL = 2-{(3-ethoxypropylimino)methyl}-6-methoxyphenol). At room temperature varying reaction conditions, cobalt-ligand ratios and use of different bases allowed unique types of coordination self-assembly. The synthetic marvel lies in the nature of aggregation with respect to the two unrelated cores in 1 and 2. Complex 1 assumes a V-shaped arrangement bound to L(-), water and a trifluoroacetate anion, while 2 grows around a central Co(II) ion surrounded by a {Co} hexagon bound to methoxide and L(-). Magnetic measurements revealed that the intermetallic interactions are antiferromagnetic in nature in the case of complex 1 and ferromagnetic in the case of 2 involving high spin cobalt(ii) ions with stabilization of the high-spin ground state in the latter case. In MeCN solutions complexes 1 and 2 showed catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBCH2) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) in air. The kinetic study in MeCN revealed that with respect to the catalytic turnover number (kcat) 2 is more effective than 1 for oxidation of 3,5-DTBCH2.
authors: Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India. dray@chem.iitkgp.ernet.in.
authors: Tufan
authors: T
authors: Singha Mahapatra
authors: Dipmalya
authors: D
authors: Basak
authors: Santanu
authors: S
authors: Chand
authors: Jeff
authors: J
authors: Lengyel
authors: Michael
authors: M
authors: Shatruk
authors: Valerio
authors: V
authors: Bertolasi
authors: Debashis
authors: D
authors: Ray
mesh_terms: D016227:Benzoquinones / Q000737:chemistry; D040761:Biomimetic Materials / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D004156:Catechol Oxidase / Q000737:chemistry*; D002396:Catechols / Q000737:chemistry; D003035:Cobalt / Q000737:chemistry*; D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D008280:Magnetics; D008958:Models, Molecular; D010084:Oxidation-Reduction
chemical_list: D016227:Benzoquinones; D002396:Catechols; D056831:Coordination Complexes; C054068:3,5-di-tert-butylcatechol; C054466:3,5-di-tert-butyl-1,2-benzoquinone; D003035:Cobalt; D004156:Catechol Oxidase