Treatment of MeMn(CO)5 with the dialkyltellurium compounds TeR2 (R = Me, Et, Pri gave the acyl complexes MeCOMn(CO)4(TeR2) in high yield. A similar reaction between EtCOMn(CO)5 and TeR2 (R = Me, Et) yielded the related complexes EtCOMn(CO)4(TeR2). When the benzyl complex BzMn(CO)5 was treated with TeR2 (R = Me, Et), BzCOMn(CO)4(TeR2) was formed initially but, on prolonged reaction in a refluxing solvent, decarbonylation occurred to form BzMn(CO)4(TeR2). Related bromo complexes BrMn(CO)4(TeR2) were obtained when BrMn(CO)5 was treated with TeR2 (R = Me, Et). Spectroscopic results indicated that all of the TeR2 substitution products have octahedral stereochemistry about manganese with a cis-configuration of the tellurium ligand and the organo or halo group. Some of the complexes were selected for assessment as possible MOCVD single source precursors. Although most of the compounds are liquids with significant volatility, they tend to dissociate when heated with release of the dialkyltellurium. Nonetheless, pyrolysis of the compounds R′COMn(CO)4(TeR2) (with R′ = Me and R = Me, Et or Pri; R′ = Et and R = Et) under typical MOCVD conditions (H2 stream, 175-225°C) produced metal films containing manganese and tellurium.