Amino Imidazolin-2-imine Ligands in Magnesium Complexes: Approaches Towards Low-Valent Mg(I) Species

René Frank, Lars Denker, Mario Barthen
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Abstract

Amino imidazoline-2-imines (AmIm) are a new class of chelating, monoanionic N,N´-donor ligands stronger than the analogous β-diketiminate ligands and give rise to five-membered metallacycles. The coordination chemistry of the monoanionic ligands 1,2-NHC=N−C6H4−NDipp− (i), cis-1,2-NHC=N−CMe=CMe−NDipp− (ii) was towards magnesium was investigated with the focus on the stabilization of low-valent magnesium(I) species, NHC = cyclo-C(NiPr2CMe)2, Dipp = 2,6-iPrC6H3. Both ligand systems (i) and (ii) form heteroleptic magnesium iodide species with were subjected to reduction. The complex [Mg(1,2-NHC=N−C6H4−NDipp)]2 was found to be insoluble, which prevented further purification. In contrast, the yield of the analogous complex [Mg(cis-1,2-NHC=N−CMe=CMe−NDipp)]2 was very low. As a significant side product the homoleptic complex [Mg(cis-1,2-NHC=N−CMe=CMe−NDipp)2] was identified.
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镁配合物中的氨基咪唑啉-2-亚胺配体:实现低价镁(I)物种的途径
氨基咪唑啉-2-亚胺(AmIm)是一类新的螯合单阴离子 N,N´-捐赠者配体,比类似的 β-二乙酰亚胺配体更强,可产生五元金属环。研究了单阴离子配体 1,2-NHC=N-C6H4-NDipp- (i)、顺式 1,2-NHC=N-CMe=CMe-NDipp- (ii) 与镁的配位化学,重点是稳定低价镁(I)物种,NHC = cyclo-C(NiPr2CMe)2,Dipp = 2,6-iPrC6H3。配体系统(i)和(ii)都会形成异性碘化镁,并被还原。发现[Mg(1,2-NHC=N-C6H4-NDipp)]2 复合物不溶于水,因此无法进一步纯化。相反,类似复合物 [Mg(cis-1,2-NHC=N-CMe=CMe-NDipp)]2 的产率非常低。作为一种重要的副产物,[Mg(cis-1,2-NHC=N-CMe=CMe-NDipp)2]同色络合物被鉴定出来。
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