abstract
A novel mononuclear Mn(III) complex, [Mn-III(L-1)Cl(H2O)]center dot H2O (1), and a tetranuclear Zn(II)-Mn(II) complex, [{Zn-2(II)(L-2)(2)Cl-2}Mn-2(II)(mu(1,1)-N-3)(2)(H2O)(2)]center dot 2H(2)O (2), have been synthesized involving azo Schiff base ligands, viz. H2L1 = (E)-6,6'-((1E,1'E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2-methoxy-4-((E)-p-tolyldiazenyl)phenol) and H2L2 = (E)-6,6'-((1E,1'E)-((2,2-dimethylpropane-1,3-diyl)bis(azanylylidene))bis(methanylylidene))bis(2-methoxy-4-((E)-p-tolyldiazenyl)phenol), respectively. The solid-state structures were determined by single crystal X-ray crystallography. In complex 1, the Mn(III) centre adopts slightly distorted octahedral geometry, while in complex 2 the Mn(II) centre residing in the outer core of the ligand adopts a distorted pentagonal bipyramidal geometry. In complex 1, the chloride ion simply acts as a terminal coligand, while in complex 2, azide ions bind the metal centres in an end-on bridging fashion to produce a tetranuclear complex. The phenoxazinone synthase-like activity of both complexes has been examined and a detailed investigation of the structure-property correlation has been performed. Whereas the mononuclear complex 1 exhibits significant phenoxazinone activity, complex 2 is almost inactive, although in both complexes labile sites are available at manganese centres for substrate binding. The present work therefore highlights the importance of higher oxidation states of manganese over nuclearity for the development of better in vitro catalysts. In addition, extensive efforts have been made to visualize and quantify all supramolecular interactions present in 1 and 2.
keywords
MULTIDENTATE LIGANDS; MIMICKING ACTIVITY; IRON; DFT; COORDINATION; ACTIVATION; CATECHOL; DIOXYGEN; CRYSTAL; ENZYMES
subject category
Chemistry
authors
Banerjee, S; Brendao, P; Bauza, A; Frontera, A; Bardelo-Oliver, M; Panja, A; Saha, A
our authors
Paula Cristina Ferreira da Silva Brandão
Assistant Researcheracknowledgements
A. S. gratefully acknowledges the financial support of this work by the DST, India (Sanction No. SB/FT/CS-102/2014, dated 18.07.2015). A. F. gratefully acknowledges the financial support of this work by the DGICYT of Spain (projects CTQ2014-57393-C2-1-P and CONSOLIDER INGENIO 2010 CSD2010-00065, FEDER funds). A. F. thanks the CTI (UIB) for free allocation of computer time.