The synthesis and characterization of rhenium nitrosyl complexes. The X-ray crystal structures of [ReBr2(NO)(NCMe)3], [Re(NO)(N5)](BPh4)2] and [ReBr2(NO)(NCMe){py-CH2-NH∼CH2CH2-N(CH2-py)2}]

► Reactions of rhenium-nitrosyl complexes with polyamine ligands have been examined. ► Rhenium(II)-nitrosyl complexes give an array of unstable products due to redox chemistry. ► Rhenium(I)-nitrosyl complex [ReBr2(NO)(NCMe)3] gives multiple products that are more stable. ► Products from reaction of [ReBr2(NO)(NCMe)3] with a pentadentate polyamine ligand are presented.