M Kanthimathi
Articles written in Journal of Chemical Sciences
Volume 102 Issue 3 June 1990 pp 418-462
Abstracts of posters presented at the symposium
Bhaskar G Maiya S M S Chauhan P Bhyrappa V Krishnan P K Bhardwaj Sabyasachi Sarkar Krishna B Pandeya Pavan Mathur Akhil R Chakravarty Birinchi K Das Digambar V Behere Sandeep Modi Samaresh Mitra Sandeep Modi Digambar V Behere Samaresh Mitra Anil Saxena Sandeep Modi Digambar V Behere S Mitra Shyamalava Mazumdar Okhil K Medhi Samaresh Mitra Shyamalava Mazumdar Samaresh Mitra Anup Madan Sandeep Modi Anil Saxena Digamber V Behere S Mitra T Pandiyan M Palaniandavar K L Narayanan H Manohar R Ramaraj C C Thomas S Rajagopal T Rajendra C Srinivasan P Ramamurthy R Roy M C Saha S Panchanan P S Roy C Balagopalakrishna M V Rajasekharan B V Agarwala S Hingorani G A Nagena Gowda Y S Ramaswamy R Halesha N M N Gowda G K N Reddy G C Saxena K L Gupta P Srivastava V D Gupta M Ray R N Mukherjee R N Mohanty K C Dash Ramesh Kapoor S Yadav V Sood P Kapoor B N Anand R Bains Usha K Aggarwal P Garge R Chikate S Padhye J M Savariault P De Loth J P Tuchgues V K Jain M A Vaidya S C Jain S Kalyan Kumar Harkesh B Singh K M Mangaonkar D N Patkar N K Jha Pankaj Sharma S K Date C E Deshpande S D Sathaye S B Deshpande H S Potdar V S Darshane A C Dash R K Nanda N N Das S Gangopadhyay P Banerjee S K Kulshreshtha P S Zacharias N Arulsamy T Ramasami V Subramanian B U Nair M Kanthimathi G Sundararajan V Shivasubramanian R G Bhattacharya S Biswas J Armstrong E M Holt A P Koley
Volume 106 Issue 3 June 1994 pp 681-689
Balachandran Unni Nair M Kanthimathi K Chandra Raj T Ramasami
The stabilization of chromium(IV) and chromium(V) in aqueous systems has now been made through designed alterations in Franck-Condon barriers for the interconversion of various oxidation states of chromium. Equatorially coordinated macrocyclic and Schiff base ligands influence the reorganizational barriers for the conversion of Cr(III)-Cr(IV)-Cr(V)-Cr(VI) couples such that Cr(IV) and Cr(V) transients of sufficiently long life time can be generated. A series of macrocyclic and Schiff base complexes of Cr(III) has been synthesised and subjected to non-complementary redox reaction with Ce(IV) or electrochemical oxidation. A Cr(IV) macrocyclic complex, Cr(Me4[14]tetraene)(H2O)24+, 1 has been generated in aqueous acidic medium, through electrochemical oxidation. The Ce(IV) oxidation of Cr(III) Schiff base complexes, diaqua[N,N′-ethylenebis(salicylideneiminato) chromium(III)], and diaqua[N,N′-propylenebis(salicylideneiminato) chromium(III)] proceed in two stages with 1 Cr:l Ce(IV) redox stoichiometry. Suffīciently long-lived Cr(IV) intermediates and Cr(V) Schiff base products have been generated. ESR evidence for the formation of Cr(V) Schiff base products and the mechanistic outcome of the oxidation of Cr(III) Schiff bases are discussed.
Volume 107 Issue 4 August 1995 pp 411-422
T Ramasami B U Nair M Kanthimathi C K Ranganathan
Some experimental approaches to seek semi-quantitative understanding of factors controlling outer sphere electron transfer reactions of some transition metal complexes have been made. The relative importance of nuclear and electronic factors to outer sphere processes has been examined. By the manipulation of Franck-Condon or nuclear factors, it has now been possible to gain access into the chemistry of chromium in unusual oxidation states. An example of a reorganisation controlled electron transfer reaction involving Cr(IV)-Cr(III) system has been demonstrated. The bimolecular rate of reduction of diperoxoaquaethylenediamine chromium(IV) and diperoxodiethylenetriamine chromium(IV) is independent of the nature of th reductant employed viz. Fe2+ or VO2+ indicating that the generation of
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