The reactions of 2,6-diformyl-4-alkyl(R)phenol (DFMP, R = CH3 or DFTBP, R = C(CH3)3) with 1,3-diamino-2-hydroxypropane (DAP) in the presence of triethylamine and copper(II) tetrafluroborate, [Cu(BF4)2] result in the formation of hexanuclear [Cu6(L-6H)(�6-BO3)(�-CH3CO2)(�-CH3O)(H2O)]BF4 (1) and [Cu6(L-6H)(�6-BO3)(DMF)2(BF4)](BF4)2(DMF) (2) complexes with an unprecedented BO33- moiety in the center of the macrocyclic cavity linked to all six copper centers. In order to prove the identity of the species present in the central cavity of the macrocycle with certainty, reactions were carried out between DFMP and DFTBP with DAP in the presence of triethylamine and copper(II) perchlorate [Cu(ClO4)2]. These reactions produce hexacopper(II) complexes (3 & 4) with BO33- moiety in the central cavity similar to complexes 1 and 2. In all these complexes six copper(II) ions are arranged in a hexagonal ring within the macrocyclic ligand, which results from the template condensation of three DFMP/DFTBP and DAP subunits. Within the ring the copper ions are bridged alternately by single and double oxygen bridges from alkoxide and phenoxide/BO33- combinations. The x-ray structures, spectrocopic, electrochemical, and magnetic properties of these complexes are reported.

Unprecedented metal catalyzed hydrolysis of BF4- ions to B(OH)3 resulting in the formation of unique hexanuclear Cu(II) complexes of macrocyclic ligands with BO33- moiety in the center of the macrocyclic ring bonded to all six metal centers

241st National Meeting (2011)

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