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=CrV Schiff base]+ has been investigated. The bimolecular rate constant for the formation of O=CrV 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).
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Kanthimathi, M., Jebanesan, D., Nair, B.U. et al. Effect of molecular association and reactivity on substitution in chromium(III)–salprn complexes. Transition Metal Chemistry 27, 895–901 (2002). https://doi.org/10.1023/A:1021320804460
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DOI: https://doi.org/10.1023/A:1021320804460