Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine and o-hydroxyacetophenone in NiII and CuII complexes

Mukherjee, Pampa ; Drew, Michael G. B. ; Ghosh, Ashutosh (2008) Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine and o-hydroxyacetophenone in NiII and CuII complexes European Journal of Inorganic Chemistry, 2008 (21). pp. 3372-3381. ISSN 1434-1948

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/ejic.20...

Related URL: http://dx.doi.org/10.1002/ejic.200800186

Abstract

Bis(o-hydroxyacetophenone)nickel (II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]•2H2O (1) of mono-condensed tridentate Schiff baseligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the NiII as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)2•4H2O furnishing the complex [NiL(NCS)] (2) and with CuCl2•2H2O in the presence of NaN3 or NH4SCN producing [CuL(N3)]2 (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)2•6H2O and Cu(NO3)2•3H2O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)2•6H2O or Ni(NO3)2•6H2O to yield [Ni(hap)2] (7). The structures of the complexes 2, 3, 5, 6 and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, NiII possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around CuII in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around CuII is square pyramidal. In both 5 and 6, the CuII atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks.

Item Type:Article
Source:Copyright of this article belongs to John Wiley and Sons, Inc.
Keywords:Nickel(II); Copper(II); Schiff Bases; Hydrolysis; Template synthesis
ID Code:108365
Deposited On:13 Oct 2017 12:45
Last Modified:13 Oct 2017 12:45

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