Alcoholysis/hydrolysis of 1,1'-carbonyldiimidazole as a means of preparing unprecedented, imidazole-containing one-dimensional coordination polymers of copper(II).
The use of 1,1'-carbonyldiimidazole, (im)(2)CO, for the synthesis of imidazolate (im(-)) and/or imidazole (Him)-containing copper(II) coordination polymers is described. The [Cu(2)(O(2)CMe)(4)(H(2)O)(2)]/(im)(2)CO reaction system in EtOH yields the new polymeric species [Cu(O(2)CMe)(im)(Him)(EtOH)](n) () and the known compound [Cu(im)(2)](n) (), depending on the reaction conditions. A mechanism for the alcoholysis/hydrolysis of (im)(2)CO is proposed. Complex comprises neutral, zigzag chains with the eta(1):eta(1):mu im(-) ligand bridging two neighbouring Cu(II) atoms. Each square pyramidal metal centre is coordinated to two imidazolate nitrogen atoms, the pyridine-type nitrogen atom of the terminal imidazole ligand, one acetate oxygen atom and the ethanol oxygen atom. The dc magnetic susceptibility data for have been analysed according to the Bonner-Fisher model for an equally spaced S = 1/2 chain, revealing moderate antiferromagnetic Cu(II)Cu(II) exchange interactions (J = -33.5 cm(-1) using the H = -2J summation operatorS(i)S(i+1) spin Hamiltonian). The reaction system Cu(NO(3))(2).3H(2)O/(im)(2)CO in EtOH leading to the preparation of known trans-[Cu(NO(3))(2)(Him)(4)] () is also described. With terephthalate(-2) (tp(2-)), instead of MeCO(2)(-), in MeOH/H(2)O the product is the new, 1D linear coordination polymer [Cu(tp)(Him)(2)(H(2)O)](n).2nH(2)O (.2nH(2)O). Adjacent square pyramidal Cu(II) atoms are singly bridged by the bis-monodentate tp(2-) ligand, while two monodentate Him groups and one H(2)O molecule complete five-coordination at each metal centre. The chains of and .2nH(2)O form interesting, hydrogen-bonded 3D networks. The combined work demonstrates the usefulness of (im)(2)CO in the preparation of interesting Cu(II) coordination polymers which can not be obtained by the use of Him.
Stamatatos
Theocharis C
TC
Department of Chemistry, University of Patras, 265 04, Patras, Greece.
Perlepes
Spyros P
SP
Raptopoulou
Catherine P
CP
Terzis
Aris
A
Patrickios
Costas S
CS
Tasiopoulos
Anastasios J
AJ
Boudalis
Athanassios K
AK