Reaction of bis(2-aminoethyl)(3-aminopropyl)amine with C6F6 and K2CO3 in DMSO yields unsymmetrical {(C6F5)HNCH2CH2}(2)NCH2CH2CH2NH(C6F5) ([N3N]H-3), The tetraamine acts as a tridentate ligand in complexes of the type H[N3N]Re(O)X (X = Cl 1, Br 2) prepared by reacting Re(O)X-3(PPh3)(2) with [N3N]H-3 and an excess of NEt3 in THF, Addition of 1 equiv of TaCH(CMe2Ph)Br-3(THF)(2) to 1 gives the dimeric compound H[N3N]ClReOReBrCl-N [N3N]H (3) in quantitative yield that contains a Re(V)=O-Re(IV) core with uncoordinated aminopropyl groups in each ligand. Addition of 2 equiv of TaCH(CMe2Ph)Cl-3(THF)(2) to 1 leads to the chloro complex [N3N]ReCl (4) with all three amido groups coordinated to the metal, whereas by addition of 2 equiv of TaCH(CMe2Ph)Br-3(THF)(2) to 2 the dibromo species H[N3N]ReBr2 (5) with one uncoordinated amino group is isolated. Reduction of 4 under an atmosphere of dinitrogen with sodium amalgam gives the dinitrogen complex [N3N]Re(N-2) (6). Single-crystal X-ray structure determinations have been carried out on complexes 1, 3, 5, and 6.