Co-C bond cleavage in the reactions of alkyl, benzyl and heteroaromaticmethyl cobaloximes with arene sulfenyl chloride: Homolytic and heterolytic pathways

The reactions of arene sulfenyl chlorides, ArSCl, (Ar = Ph, C6Cl5, 2,4 (NO2 )(2)C6H3) with organocobaloximes, RCo(dmgH)(2)Py, (R = alkyl, benzyl and he teroaromaticmethyl) were carried out under thermal and photochemical condit ions. A variety of organic and organometallic products are formed depending upon the substrate cobaloxime. For 3-methoxybenzyl and heteroaromaticmethy l cobaloximes the results suggest that they represent a unique class of cob aloximes whereby both the aromatic ring as well as the Co-C bond are highly activated towards attack by the arene sulfenyl chloride. Both homolytic as well as heterolytic pathways are operative. (C) 1999 Elsevier Science S.A. All rights reserved.