Nickel(II), Cobalt(II), Copper(II) & Palladium(II) Complexes of 1,2-Di-(o-salicylaldiminophenylthio) ethane

275-27

Complexes of hexadentate NSO donor ligands - III. Nickel(II) complexes of 1,3-di(o-salicylaldiminophenylthio)propane and 1,2-di(o-salicylaldiminophenylthio)xylene

Nickel(II) complexes of the hexadentate N2S2O2 donor ligands, 1,3-di(o-salicylaldiminophenylthio)propane (H(2)DSALPTP) and 1,2-di(o-salicylaldiminophenylthio)xylene (H(2)DSALPTX) have been synthesised and characterised. H(2)DSALPTP reacted with NiCl2.6H(2)O or Ni(ClO4)(2).6H(2)O in presence of ammonia to give the complex [Ni(DSALPTP)] (1). H(2)DSALPTX reacted smoothly with N(ClO4)(2) to yield the corresponding complex [Ni(DSALPTX)] (2). The ligand did not react with NiCl2 in the absence of ammonia but in its presence produced the complex (2). The molecular and crystal structure;of [Ni(DSAL PTX)] exhibits a very unusual deployment of the six donor sites of the ligand. It crystallises in the orthorhombic system with space group P2(1)2(1)2(1). In dichloromethane solution both the complexes are found to exhibit Ni(II)/Ni(III) redox couples in their cyclic voltammograms at room temperature with E-1/2 values 0.87 and 0.78 V (vs. Ag/AgCl). (C) 1998 Elsevier Science Ltd. All rights reserved

Complexes with N, S donor ligands: Part II-Nickel (II), copper (II), cobalt (II), iron (III) and palladium (II) complexes of 2, 4-bis(2'-mercaptophenylimino)- pentane and 2-(2-mercaptophenyl)imino-4-pentanone and their reactions with alkyl and aryl halides leading to the formation of macro cycles

952-955The in situ reactions of a mixture of 2, 4-pentanedione and 2-aminobenzenethiol with Ni(II) and Pd(II) salts yield complexes of the type [M2(MPIP)2] where H2MPIP is the schiff base 2-(2-mercaptophenyl)imino- 4-pentanone obtained by condensation of one molecule of the ketone with one molecule of the amine, On the other hand, similar reactions with Co(II), Fe(III) and Cu(II) salts give the complexes [Co(PDMPI), [Fe(PDMPI) CI] and [Cu2(PDMPI)CI2] where H2PDMPI is the schiff base obtained by the condensation of two molecules of the amine with one molecule of the ketone. [Fe(pDMPI)Cl] smoothly reacts with bifunctional alkylating agents like 1, 2-dibromoethane and α, α'-dibromo-o-xylene to form the macrocyclic complexes of {S, S'-ethylene-2, 4-bis(2'- ercaptophenylimino)pentane} iron(III), [Fe(EPDMPI)Cl]Br2 and {S, S'-o--xylyl-2, 4-bis(2' -mercaptophenylimino)pentane} iron (III), [Fe(XPDMPI)CI]Br2 respectively as a result of the alkylation of the two coordinated mercaptide groups of the complex

A very rare hydrogen-bridged hexanuclear CuII complex containing a triangular Cu3O core capped by an unusual triply coordinated perchlorate anion

An unusual hexanuclear Cu-II complex, [{[Cu(NHDEPO)](3)(mu(3)-O)(O3ClO)}(2)(mu-H)]center dot 7ClO(4)center dot 4H(2)O (1) was prepared starting from Cu(ClO4)(2)center dot 6H(2)O and the oxime-based Schiff base ligand NHDEPO (= 3-[3-(diethylamino)propylimino]butan-2-one oxime). Structural characterization of the complex reveals that it consists of two triangular Cu3O units, the copper ions being at the corners of an equilateral triangle, separated by an O center dot center dot center dot O distance of 2,447(5) angstrom, held together solely by a proton. In each triangle, the copper atoms are in square-pyramid environments. The equatorial plane consists of the bridging oxygen of the central OH-(O2-) group together with three atoms (N, N, O) of the Schiff base. All Unusual triply coordinated perchlorate ion (mu(3)-kappa O:kappa O':kappa O '') interacts in axial position with the three copper ions, Variable-temperature (2-300 K) magnetic susceptibility measurements show that complex 1 is antiferromagnetically Coupled (J = -148 cm(1-)). The EPR data at low temperature clearly indicates the presence of spin frustration phenomenon in the complex

A very rare hydrogen-bridged hexanuclear Cu^II complex containing a triangular Cu₃O core capped by an unusual triply coordinated perchlorate anion

An unusual hexanuclear CuII complex, [{[Cu(NHDEPO)]3(μ 3-O)(O3ClO)}2(μ-H)]•7ClO4•4H2O (1) was prepared starting from Cu(ClO4)2•6H2O and the oxime-based Schiff base ligand NHDEPO (= 3-[3-(diethylamino)propylimino]butan-2-one oxime). Structural characterization of the complex reveals that it consists of two triangular Cu3O units, the copper ions being at the corners of an equilateral triangle, separated by an O•••O distance of 2.447(5) Å, held together solely by a proton. In each triangle, the copper atoms are in square-pyramid environments. The equatorial plane consists of the bridging oxygen of the central OH– (O2–) group together with three atoms (N, N, O) of the Schiff base. An unusual triply coordinated perchlorate ion (μ 3-κO:κO′:κO″) interacts in axial position with the three copper ions. Variable-temperature (2–300 K) magnetic susceptibility measurements show that complex 1 is antiferromagnetically coupled (J = –148 cm–1). The EPR data at low temperature clearly indicates the presence of spin frustration phenomenon in the complex