The new hydrazine 5H-dibenzo[b,f]azepin-5-amine (2) reacts with P- and Si-electrophiles via deprotonation to afford P(III)-, P(V)-, and TMS-hydrazides 3-8 and with carbonyl electrophiles via acid-free condensation to the N-substituted hydrazones 9-12 that are potential N-alkene ligands. While β-ketohydrazone 9 and α-dihydrazone 10 react with [Mes(Cu)]4, [Cu(NCCCH3)4]2PF6, and FeCl2(THF)1.5 to afford complexes devoid of alkene interaction, [Cu(OTf)]2·C6H6 reacts with the α-keto hydrazone 11 or with N,N dimethyl-hydrazone 12 to form the neutral dimeric Cu(I) complex 18 with bridging Cu(I)-alkene interactions or the tetrahedral cationic complex 19 in which 12 binds as a bidentate hydrazone-alkene ligand, respectively. The surprising stability of the alkene coordination in complexes 18 and 19 prevents substitutions with, e.g., PPh3.