Synthesis, structure, and reactivity of bis(N,N′-bis(2-hydroxybenzylidene)-2-hydroxyphenylmethanediaminato)zirconium(IV), a Schiff base complex with 6,4,6-membered chelate rings

摘要: Abstract The title complex Zr(dshpm)2 has been successfully prepared by heating a 1:2 mole ratio of Zr(OBun)4 and the free ligand in absolute ethanol. It is mononuclear eight-coordinate solid state with dodecahedral coordination sphere. two O,N,N,O donor atom quadridentate Schiff base ligands each form 6,4,6-membered chelate rings. As expected, change ring sizes from 6,5,6- to 6,4,6- resulted significantly more labile complex, as indicated TLC NMR heated solutions its subsequent chemical reactions. 0.010 A shorter average ZrN bond distance was not anticipated, appears result zirconium atom's preference that oxygen atoms occupy certain locations. Preparations heteroleptic complexes were undertaken evaluate potential compound synthon. new fluorine-substituted homoleptic Zr also prepared, for comparison purposes. Despite reasonable stability air, decomposition labilized Hdshpm(2-) on silica gel solution interfered purifications desired products.