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- Title
Magnesium(I) Dimers as Reagents for the Reductive Coupling of Isonitriles and Nitriles.
- Authors
Ma, Mengtao; Stasch, Andreas; Jones, Cameron
- Abstract
The reactivity of two β-diketiminate coordinated magnesium(I) dimers, [LMgMgL], L=[(RNCMe)2CH]−, R=C6H3 iPr2-2,6 (DipNacnac−) or mesityl (MesNacnac−), towards a series of isonitriles and nitriles have been examined. Reactions with the isonitriles, RNC: (R= tBu or C6H3Me2-2,6 (Xyl)), led to reductive CC couplings and the formation of [{(DipNacnac)Mg}2{μ-(XylN=C-)2}] and [{(MesNacnac)Mg}2{μ-( tBuN=C-)2}], or a reductive NC cleavage and the generation of the magnesium cyanide complex, [{(DipNacnac)Mg(μ-CN)}3]. Reactions of the magnesium dimers with benzonitrile, PhCN, afforded the CC-coupled products, [(DipNacnac)Mg[μ-{N=C(Ph)-}2]Mg(NCPh)(DipNacnac)], and [{{(MesNacnac)Mg}2[μ-{N=C(Ph)-}2]}2], whereas the reductive CC cleavage of tBuCN gave rise to a mixture of [(DipNacnac)Mg( tBu)(NC tBu)] and [{(DipNacnac)Mg(μ-CN)}3]. In contrast, a combination of net nitrile isomerization and CC coupling processes was involved in the reduction of Me3SiCN, which yielded [{(DipNacnac)Mg}2{μ-(Me3SiN=C-)2}]. All new compounds were crystallographically and spectroscopically characterized. The outcomes of the reported reactions were found to be dependent upon both the steric bulk of the magnesium(I) reagent, and the nature of the isonitrile/nitrile substituent. This combined with a high degree of selectivity for the reactions, indicates that magnesium(I) dimers may find use by organic and organometallic chemists as viable alternatives to currently available reducing agents that are utilized for the reduction of unsaturated organic substrates.
- Publication
Chemistry - A European Journal, 2012, Vol 18, Issue 34, p10669
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201201030