Syntheses and Reactivity Studies of Square-Planar Diamido鈥揚yridine Complexes Based on Earth-Abundant First-Row Transition Elements

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• 作者：Owen T. Summerscales ; Jamie A. Stull ; Brian L. Scott ; John C. Gordon
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 20, 2015
• 年：2015
• 卷：54
• 期：14
• 页码：6885-6890
• 全文大小：331K
• ISSN：1520-510X

文摘

The new square-planar complexes M[NNN](pyridine) (M = Fe (1), Co(2); NNN = 2,6-bis(2,6-diisopropylphenylamidomethyl)pyridine) were synthesized and fully characterized to investigate small molecule activation on this platform and also associated ligand innocence. The equatorial pyridine solvent moiety could not be removed; a new bis-ligand species Co[NNN.H]₂ (3) was synthesized in low yield while attempting to make the base-free derivative. Attempts to prepare the Ni analogue of 1 and 2 instead yielded crystals of a di-imino鈥損yridine complex Ni[PDI]Cl (4) (PDI = 2,6-bis(2,6-diisopropylphenyliminomethyl)pyridine), following loss of methylene backbone hydrogen atoms. Structural analysis indicates that the PDI ligand is a mono-anionic radical. This susceptibility of the ligand to oxidative dehydrogenation was also shown when the reaction of 2 with 2 equiv of trityl chloride yielded a new complex with an asymmetric imino鈥揳mino pyridine ligand Co[NNN鈥瞉Cl₂ (5) (NNN鈥?= 2-(2,6-(diisopropylphenyliminomethyl)-6-(diisopropylphenylamidomethyl)-pyridine) in good yield.