Abstract

Photochemical reaction of (?5-C5 Me5)Re(CO)3, with 2,4,5-trichloroanisole and 3,4,5-trichlorotrifluoromethylbenzene yields (?5-C 5Me5)Re(CO)2(C6H2 Cl2(MeO))Cl (1) and (?5-C5Me 5)Re(CO)2(C6H2Cl2 (CF3))Cl, (2) formed by insertion of the fragment (?5-C5Me5)Re(CO)2 into the C-Cl bond of the chloroarenes. The C-Cl bond activation of trichloroanisole occurs at the chlorine ortho respect to the methoxy group as revealed by the X-ray structure of 1. In the case of the reaction with C6H2Cl3(CF3), 1H-NMR spectroscopy indicates that only the C-Cl bond meta respect to CF3 group is cleaved. Complex 1 was isolated as the trans isomer while 2 was obtained as an isomeric mixture (trans-2 and cis -2). The stereochemistry of these complexes has been assigned by IR and 13C-NMR spectroscopies and supported by X-ray crystallography for 1. © 2003 Elsevier B.V. All rights reserved.