Two new routes have been developed to generate manganese-chelated amides from imine and carbon monoxide building blocks. The reaction of (CO) 5 MnR (R ) CH 3 , Ph) with (ptolyl)(R 1 )dNR 2 (R 1 ) H, t Bu; R 2 ) alkyl, H) results in the generation of the cyclometalated imine complexes (CO) 4 Mn[η 2 -4-CH 3 -2-(C(R 1 )dNR 2 )-C 6 H 3 ] in 50-84% isolated yield. However, when the reaction of (p-tolyl)(H)CdNCH 3 with (CO) 5 MnCH 3 is performed in the presence of AlCl 3 , the product of sequential carbon monoxide and imine insertion is generated in 35% yield: (CO) 4 Mn[η 2 -C(H)(p-tolyl)N(CH 3 )COCH 3 ]. The addition of PPh 3 to the latter complex results in replacement of a carbonyl ligand and formation of the isolable fac-(CO) 3 (PPh 3 )-Mn[η 2 -C(H)(p-tolyl)N(CH 3 )COCH 3 ]. In an alternative route to metal-bound amides, the oxidative addition of the N-acyl iminium salt (p-tolyl(H)CdN(CH 3 )COPh + Clto (CO) 5 Mn -Na + has been found to lead to the generation of the product of subsequent CO insertion, (CO) 4 Mn-[η 2 -COC(H)(p-tolyl)N(CH 3 )COPh]. The latter represents the first example of a acyl-bound transition-metal-chelated R-amino acid complex and has been characterized by X-ray crystallography. Preliminary reactivity studies demonstrate that (CO) 4 Mn[η 2 -COC(H)(ptolyl)N(CH 3 )COPh] reacts with PPh 3 to generate the unchelated cis-(CO) 4 (PPh 3 )Mn[COC-(H)(p-tolyl)N(CH 3 )COPh], while reaction with NaBH 4 leads to the liberation of the amide (p-tolyl)CH 2 N(CH 3 )COPh, rather than the amino acid residue.