Octalithium, Tetrasodium, and Decalithium Compounds Based on Pyrrolyl Ligands: Synthesis, Structures, and Activation of the C–H Bonds of Pyrrolyl Rings and C═N Bonds of a Series of Ligands by Organolithium Reagents
Chaohong Jia, Yeye She, Yanhua Lu, Mengxiang Wu, Xiaohan Yang, Ling Chen, and Yahong Li*（李亚红）
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People’s Republic of China
Inorg. Chem. 2023, 62, 14072−14085
Abstract：The organometallic compounds of lithium ions have garnered continuous interest as indispensable precursors for the syntheses of organometallic complexes of main-group metals, transition metals, lanthanide metals, and actinide metals. In this work, we present a strategy for the preparation of a series of polynuclear lithium complexes. This methodology features the utilization of organolithium reagents both as metal sources to coordinate with the ligands and as nucleophilic reagents to undergo nucleophilic addition to the C═N bonds of the ligands. Reaction of a ligand HL1 [HL1 = 2-(((1-(2-(dimethylamino)ethyl)-1H-pyrrol-2-yl)methylene)amino)phenol] with n-BuLi produced complex [Li8(L1a)4]·1.5Tol (1·1.5Tol) [H2L1a = 2-((1-(1-(2-(dimethylamino)ethyl)-1H-pyrrol-2-yl)pentyl)amino)phenol]. One prominent feature regarding the formation of 1·1.5Tol is the occurrence of nucleophilic addition of n-BuLi to the C═N bond of HL1, leading to the generation of a new [L1a]2– ligand that contains both aminophenol and 1-(2-pyrrolyl)alkylamine scaffolds. The developed protocol can be adapted to a series of organolithium reagents. Compounds [Li8(L1b)4] (2) and [Li8(L1c)4] (3) were afforded by treatment of HL1 with sec-BuLi and LiCH2SiMe3, respectively. Reaction of an analogous ligand HL2 [HL2 = 2-(((1-(2-(dimethylamino)ethyl)-1H-pyrrol-2-yl)methylene)amino)-4-methylphenol] with n-BuLi generated compound [Li8(L2a)4] (4). C═N bond activation was not observed in the reaction of HL1 with NaOtBu, and the complex [Na4(L1)4]·Tol (5·Tol) was obtained. A decanuclear complex [Li10(L3a)2(L3b)2] (6) was also prepared via the reaction of HL3 [HL3 = 2-(2-((((1H-pyrrol-2-yl)methylene)amino)methyl)-1H-pyrrol-1-yl)-N,N-dimethylethan-1-amine] with t-BuLi. A remarkable feature in terms of the synthesis of 6 is the simultaneous occurrence of hydrogen atom abstraction from the C–H bond of the pyrrolyl ring and nucleophilic addition to the C═N bond of the HL3 ligand by t-BuLi. A series of amines containing biologically and physiologically important moieties were achieved by hydrolysis of the crude products from the reactions of the HL1–HL3 ligands and organolithium reagents. This work provides an efficient approach to high-nuclearity lithium compounds as well as a series of amines.
链接：//pubs.acs.org/doi/10.1021/acs.inorgchem.3c02208
