Abstract The syntheses of seven bridgehead diazabicycloalkanes are reported. The bridges are represented by either a thioether chain and two 3-hexyne units (4 and 6–8), one selenoether chain and two 3-hexyne units (5), or one dithioether chain and two 4, 4′- diethylbiphenyl units (9, 10). X-ray investigations reveal for 4–10 the in/in conformation at the bridgehead nitrogen atoms. Reactions with Cu I triflate yield the endohedral Cu I ...