The role of methanol molecule in supramolecular assembling of [MoO2L(CH3OH)] · CH3OH and [MoO2L(CH3OH)] Schiff base type complexes (CROSBI ID 628360)
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Podaci o odgovornosti
Katava, Robert ; Pavlović, Gordana ; Cindrić, Marina
engleski
The role of methanol molecule in supramolecular assembling of [MoO2L(CH3OH)] · CH3OH and [MoO2L(CH3OH)] Schiff base type complexes
Investigations of Schiff base molybdenum(VI) complexes have been stimulated by discovery of molybdenum in a number of redox enzymes[1] and their efficiency as catalysts both in heterogeneous and homogenous reactions[2]. Reactions of tridentate O, N, O Schiff base ligands H2L with [MoO2(acac)2] afforded a series of distorted octahedral cis-MoO22+ complexes of the type [MoO2L(CH3OH)] · CH3OH (1-4) and [MoO2L(CH3OH)] (5). Coordinated CH3OH molecule, positioned trans to oxido oxygen atom, could be readily removed from first coordination sphere of molybdenum(VI) cation, yielding a [MoO2(L)] intermediate responsible for catalytic activation of substrates during Lewis acid catalyzed transformations. The supramolecular architecture of complexes is dominated by two types of hydrogen bonds (HB): O −H···O and C−H···O. The supramolecular motif shaped by O−H···O HB in 2, 3 and 4 differs in comparison with that formed by the same type of HB in 1. The infinite chains in 2, 3 and 4 are shaped via the O−H···O HB which include the coordinated methanol oxygen atom, MeOH solvent molecule and the oxido oxygen atom of the complex molecule. On the contrary, the supramolecular dimers in 1 are formed by two molecules of solvent CH3OH and two complex molecules via the phenolate oxygen atom and oxygen atom from coordinated CH3OH. Formed dimers are condensed with both sides with complex molecules via C−H···O intermolecular hydrogen bond which form centrosymmetric puckered 15-membered ring. Since the complex 4 does not contain solvent molecule of crystallization, the main supramolecular synthon formed via O−H···O hydrogen bond is centrosymmetric dimer between the –OH group of coordinated methanol and the oxygen donor atom of five-membered chelate ring of another complex molecule. The determination of supramolecular role of MeOH molecules is essential in the context of complexes solubility and their catalytic activity in the conditions of epoxidation. [1] M. J. Barber, P. J. Neame, J. Biol. Chem. 265 (1990) 20912-20915. [2] J. Pisk, D. Agustin, V. Vrdoljak, R. Poli, Adv. Synth. Catal. 353 (2011) 2910-2914.
molybdenum(VI) complexes; supramolecular assembling; catalytic activity
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Podaci o prilogu
448-449.
2015.
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objavljeno
Podaci o matičnoj publikaciji
29th European Crystallographic Meeting, Book of Abstracts
Podaci o skupu
29th European Crystallographic meeting
poster
23.08.2015-28.08.2015
Rovinj, Hrvatska