The first examples of SmI2 mediated radical cyclizations of ketimines have been achieved with η6-arene-Cr(CO)3 complexes bearing ketimine sidechains. The cyclization products were obtained in high yield and with significant diastereoselectivity. The reactions seem to proceed via addition of azaketyl-type radicals to the complexed arenes to form 17 VE intermediates which are trapped by single electron transfer to give the corresponding (anionic) 18 VE species.