The tridentate bis-phosphinimine ligands O(1,2-C6H4N
PPh3)21, HN(1,2-C2H4N
PR3)2 (R = Ph 2, iPr 3), MeN(1,2-C2H4N
PPh3)24 and HN(1,2-C6H4N
PPh3)25 were prepared. Employing these ligands, monometallic Pd and Ni complexes O(1,2-C6H4N
PPh3)2PdCl26, RN(1,2-CH2CH2N
PPh3)2PdCl][Cl] (R = H 7, Me 8), [HN(1,2-CH2CH2N
PiPr3)2PdCl][Cl] 9, [MeN(1,2-CH2CH2N
PPh3)2PdCl][PF6] 10, [HN(1,2-CH2CH2N
PPh3)2NiCl2] 11, [HN(1,2-CH2CH2N
PR3)2NiCl][X] (X = Cl, R = iPr 12, X = PF6, R = Ph 13, iPr 14), and [HN(1,2-C6H4N
PPh3)2Ni(MeCN)2][BF4]Cl 15 were prepared and characterized. While the ether-bis-phosphinimine ligand 1 acts in a bidentate fashion to Pd, the amine-bis-phosphinimine ligands 2–5 act in a tridentate fashion, yielding monometallic complexes of varying geometries. In contrast, initial reaction of the amine-bis-phosphinimine ligands with base followed by treatment with NiCl2(DME), afforded the amide-bridged bimetallic complexes N(1,2-CH2CH2N
PR3)2Ni2Cl3 (R = Ph 16, iPr 17) and N(1,2-C6H4N
PPh3)2Ni2Cl318. The precise nature of a number of these complexes were crystallographically characterized.