Methods of forming ruthenium-containing films by atomic layer deposition and/or chemical vapor deposition are provided. The methods comprise delivering at least one precursor and an oxygen-free co-reactant, such as hydrazine or alkylhydrazine, to a substrate to form a ruthenium-containing film, wherein the at least one precursor corresponds in structure to Formula (I): (L)Ru(CO)3, wherein L is selected from the group consisting of a linear or branched C2-C6-alkenyl and a linear or branched C1-C6-alkyl; and wherein L is optionally substituted with one or more substituents independently selected from the group consisting of C2-C6-alkenyl, C1-C6-alkyl, alkoxy and NR1R2; wherein R1 and R2 are independently alkyl or hydrogen; and annealing the ruthenium-containing film under vacuum or in the presence of an inert gas such as Ar, N2, or a reducing gas such as H2 or a combination thereof.