Several new Ru(II) complexes of tris(2-aminoethyl)amine (Tren) and diethylenetriamine (Dien) have been prepared using Ru(PPh₃)₃Cl₂ and (Me₄N)₂[Ru(Phen)Cl₄] as starting complexes. The Tren-based complexes are significant in that only one other Ru(II)-Tren complex has been reported previously. The reaction of Tren or Dien with Ru(PPh₃)₃Cl₂ leads to the formation of either the [Ru(Tren)(PPh₃)Cl]Cl or the [Ru(Dien)(PPh₃)Cl₂] complex, of which the latter then reacts further with a heterocyclic diimine (N�N) ligand to yield [Ru(Dien)(PPh₃)(N�N)]Cl₂. Addition of Tren or Dien to solutions of the (Me₄N)₂[Ru(Phen)Cl₄] complex replaces the coordinated chlorides with the N-donor ligand, forming [Ru(Tren)Phen](ClO₄)₂ and [Ru(Dien)(Phen)Cl]Cl respectively. All of the complexes are luminescent with several emitting in the visible region. Their redox chemistry shows a single-electron Ru(II)→Ru(III) oxidations over a wide range of potentials. Additionally, we have synthesized two Ru(II) complexes from the heteroaromatic Tren analogue, tris((1-ethyl-2'-benzimidazolyl)methyl)amine (EtNTB). Due to the alkylation of the EtNTB ligand, benzimidazolate-based NTB-bridging is thwarted, and so [Ru(EtNTB)(Phen)](ClO₄)₂ and [Ru₂(EtNTB)₂(mu-Cl)₂]Cl₂ are formed.