Complexes of the form TpRe(CO)(MeIm)(
2-pyr) and TpW(NO)(PMe
3)(
2-pyr) (where pyr =1-methylpyrrole, 2-methylpyrrole, and 2,5-dimethylpyrrole) were prepared and combined with a rangeof potential dipolarophiles. In several cases a dipolar cycloaddition resulted in the formation of7-azanorbornene complexes (one crystal structure for each metal is presented), but attempts to developa general route to the organic bicyclic system were unsuccessful. Using the complex [Os(NH
3)
5(
2-pyrrole)]
2+ an organic cycloadduct was successfully prepared with dimethyl fumarate, and this complexwas elaborated into advanced synthons to several naturally occurring pyrrolizidines.