Paper
Low-Valent Aminopyridinato Chromium Methyl Complexes via Reductive Alkylation and via Oxidative Addition of Iodomethane by a Cr–Cr Quintuple Bond
Published Feb 9, 2015 · A. Noor, S. Schwarz, R. Kempe
Organometallics
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Abstract
The reaction of 1 equiv of the deprotonated (sterically demanding) aminopyridine Ap*-H (Ap*-H = (2,6-diisopropylphenyl)-[6-(2,4,6-triisopropylphenyl)pyridin-2-yl]amine) with [CrCl3(thf)3] led selectively to the monomeric complex [Ap*CrCl2(thf)2]. Methylation of [Ap*CrCl2(thf)2] by methyllithium gave rise to a mixture of a dichromium methylidene and a dichromium methyl complex. Alkylation of [Ap′CrCl2(thf)2] (Ap′-H = (2,6-diisopropylphenyl)-[6-(2,6-dimethylphenyl)pyridin-2-yl]amine) afforded selectively the dimethyl complex [Ap′2CrCr(CH3)2]. In addition to reductive alkylation, oxidative addition can be used to synthesize chromium methyl complexes. Selective oxidative addition was observed when CH3I was reacted with the quintuply bonded CrI dimer [Ap′CrCrAp′]. Here, the Grignard-like Cr2 compound [Ap′2CrCr(μ-I)(μ-CH3)] was formed. DFT calculations were performed to investigate the electronic structure of the organometallic complexes.
Low-valent aminopyridine can be converted into chromium methyl complexes via reductive alkylation and oxidative addition, yielding various organometallic compounds with diverse electronic structures.
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