Insertion of Imines and Carbon Monoxide into Manganese−Alkyl Bonds: Synthesis and Structure of a Manganese−α-Amino Acid Derivative
作者:Danny Lafrance、Jason L. Davis、Rajiv Dhawan、Bruce A. Arndtsen
DOI:10.1021/om000745d
日期:2001.3.1
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)CNCH3 with (CO)5MnCH3 is
已经开发出两条新的路线,从亚胺和一氧化碳的结构单元中生成锰螯合的酰胺。(CO)5 MnR(R = CH 3,Ph)与(对甲苯基)(R 1)NR 2(R 1 = H,t Bu; R 2 =烷基,H)的反应导致生成环金属亚胺络合物(CO)4的Mn [η 2 -4-CH 3 -2-(C(R 1)NR 2)-C 6 H ^ 3 ]在50-84%的分离收率。但是,当(p-甲苯基)(H)C NCH反应时3与(CO)5 MNCH 3中的AlCl存在下进行3,在35%的产率生成顺序一氧化碳和亚胺插入的产物:(CO)4的Mn [η 2 -C(H)(p -甲苯基)N(CH 3)COCH 3 ]。PPH的添加3到后者复杂结果在更换可分离的羰基配位体和形成FAC - (CO)3(PPH 3)的Mn [η 2 -C(H)(p -甲苯基)N(CH 3)婴儿床3]。在金属结合的酰胺的替代路线中,N-酰基亚胺盐的氧化加成(p