Insertion of Imines and Carbon Monoxide into Manganese−Alkyl Bonds:  Synthesis and Structure of a Manganese−α-Amino Acid Derivative

• Published in: Organometallics Vol. 20; no. 6; pp. 1128 - 1136
• Main Authors: Lafrance, Danny, Davis, Jason L, Dhawan, Rajiv, Arndtsen, Bruce A
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 19.03.2001; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Physical Sciences; Science & Technology; CATALYZED ALTERNATING COPOLYMERIZATION; SEQUENTIAL INSERTION; MECHANISTIC ASPECTS; PENTACARBONYL; METHYL; COMPLEXES; AMIDOCARBONYLATION; EFFICIENT SYNTHESIS; PALLADIUM-ACYL BONDS; MIGRATION CO INSERTION
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om000745d

Two new routes have been developed to generate manganese-chelated amides from imine and carbon monoxide building blocks. The reaction of (CO)5MnR (R = CH3, Ph) with (p-tolyl)(R1)NR2 (R1 = H, tBu; R2 = alkyl, H) results in the generation of the cyclometalated imine complexes (CO)4Mn[η2-4-CH3-2-(C(R1)NR2)-C6H3] in 50−84% isolated yield. However, when the reaction of (p-tolyl)(H)CNCH3 with (CO)5MnCH3 is performed in the presence of AlCl3, the product of sequential carbon monoxide and imine insertion is generated in 35% yield:  (CO)4Mn[η2-C(H)(p-tolyl)N(CH3)COCH3]. The addition of PPh3 to the latter complex results in replacement of a carbonyl ligand and formation of the isolable fac-(CO)3(PPh3)Mn[η2-C(H)(p-tolyl)N(CH3)COCH3]. In an alternative route to metal-bound amides, the oxidative addition of the N-acyl iminium salt (p-tolyl(H)CN(CH3)COPh+Cl- to (CO)5Mn-Na+ has been found to lead to the generation of the product of subsequent CO insertion, (CO)4Mn[η2-COC(H)(p-tolyl)N(CH3)COPh]. The latter represents the first example of a acyl-bound transition-metal-chelated α-amino acid complex and has been characterized by X-ray crystallography. Preliminary reactivity studies demonstrate that (CO)4Mn[η2-COC(H)(p-tolyl)N(CH3)COPh] reacts with PPh3 to generate the unchelated ci s-(CO)4(PPh3)Mn[COC(H)(p-tolyl)N(CH3)COPh], while reaction with NaBH4 leads to the liberation of the amide (p-tolyl)CH2N(CH3)COPh, rather than the amino acid residue.