Reactions of Dianionic α-Diimine-Supported Dimagnesium(I) Compound [K(THF)3]2[LMg-MgL] with Nitriles

Jijiang Wang, Juju Wang, Lingyi Shen, Yanxia Zhao*, Biao Wu, Xiao Juan Yang

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)

Abstract

The Mg-Mg-bonded compound, [K(THF)3]2[LMg-MgL] (1, L = [(2,6-iPr2C6H3)NC(Me)]2 2-), exhibits good reactivity toward a series of nitriles (RCN). Reaction of 1 with 2.0 equiv of Me3SiCN proceeded through reductive Si-C(CN) bond cleavage to generate the cyanide ions (CN-), which serve as bridges to link the tetrameric complex [L4Mg4(μ-CN)4K4(THF)6] (2). When more (3.0 equiv) of the nitrile substrates Me3SiCN or tBuCN were reacted with 1, both Si-C(CN) [or C-C(CN)] bond cleavage and terminal coordination of the nitriles occurred, leading to the tetramers [L4Mg4(μ-CN)4(RCN)2K4(THF)4] (R = Me3Si, 3 and R = tBu, 4). More interestingly, reaction of precursor 1 with 2.0 equiv of isobutyronitrile (iPrCN) or cyclohexyl nitrile (CyCN) that has α-hydrogen atoms afforded the dinuclear complexes [{K(THF)2LMg(μ-N=C=CMe2)}2] (6) and [{K(Tol)LMg(μ-N=C=CC5H10)}2] (7) with bridging keteniminate ligands, representing a rare reductive deprotonation pathway for nitriles. All products were characterized by X-ray diffraction, NMR, and infrared spectra and density functional theory computations.

Original languageEnglish
Pages (from-to)2674-2682
Number of pages9
JournalOrganometallics
Volume38
Issue number13
DOIs
Publication statusPublished - 8 Jul 2019
Externally publishedYes

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