Effect of molecular association and reactivity on substitution in chromium(III)-salprn complexes

Kanthimathi, Mookandi and Jebanesan, Daniel and Nair, Balachandran Unni and Jeyakanthan, Jeyaraman (2002) Effect of molecular association and reactivity on substitution in chromium(III)-salprn complexes. In: Transition Metal Chemistry, 27 (8). pp. 895-901.

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Abstract

A new chromium(III)-Schiff base complex, [Cr(5-chlorosalprn)(H2O)(2)]ClO4, where salprn=N,N'-propylenebis(salicylideneimine) has been prepared and characterized by electrospray ionization mass spectrometric (ESIMS) analysis and other spectroscopic techniques. Single crystal X-ray data reveal that the complex assumes a trans-diaquo structure, [Cr(C17H18Cl2N2O4)]ClO4.H2O. The effect of phenyl ring substituents on the rate of formation of [O=Cr-V Schiff base](+) has been investigated. The bimolecular rate constant for the formation of O=Cr-V species by the [Cr(Schiff base)(H2O)(2)]ClO4, where the Schiff base=salprn, (1) and 5-chlorosalprn, (2) with PhOI was compared. In the case of (2) the rate was found to be faster by an order of magnitude at pH=4 compared to (1). The introduction of a chloro-substituent on the phenyl ring not only influences the rate of redox reactivity but also the pKa values of aquo ligands of the complexes, indicating the difference in the electronic environment around the metal ion in both (1) and (2).

Item Type:	Journal Article
Publication:	Transition Metal Chemistry
Publisher:	Springer
Additional Information:	Copyright of this article belongs to Springer.
Department/Centre:	Division of Biological Sciences > Molecular Biophysics Unit
Date Deposited:	20 Jul 2011 08:45
Last Modified:	20 Jul 2011 08:45
URI:	http://eprints.iisc.ac.in/id/eprint/39156

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