Kennedy Dominic B, Pearce Kyle G, Morris Louis J, Mahon Mary F, Jones Cameron, Hill Michael S
Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800, Australia.
Chemistry. 2025 Feb 12;31(9):e202404160. doi: 10.1002/chem.202404160. Epub 2024 Dec 13.
The dimeric calcium and magnesium hydrides, [(BDI)AeH] [BDI=HC{(Me)CNDipp}, Dipp=2,6-i-PrCH; Ae=Mg or Ca] do not react with PhGeH in non-coordinating solvent. Addition of THF, however, induces deprotonation and access to monomeric Ae-germanide complexes, [(BDI)Ae{GePh}(THF)], both of which have been structurally characterized. Although this process is facile when Ae=Ca, the analogous magnesium-based reaction requires heating to temperatures >100 °C, under which conditions germanide formation is complicated by THF ring opening and the generation of an alkaline earth germyl-C-terminated n-butoxide, [(BDI)Mg{μ-O(CH)GePh}]. Reactions of [(BDI)Ca{GePh}(THF)] with N,N'-di-isopropylcarbodiimide and benzophenone provide the respective germylamidinate and germylalkoxide derivatives, [(BDI)Ca{(i-PrN)CGePh}(THF)] and [(BDI)Ca{OC(GePh)Ph}(THF)], demonstrating its potential as a well-defined and soluble source of the [PhGe] anion in nucleophilic addition reactions.
二聚氢化钙和氢化镁，[(BDI)AeH] [BDI = HC{(Me)CNDipp}，Dipp = 2,6 - i - Pr₂C₆H₃；Ae = Mg或Ca] 在非配位溶剂中不与PhGeH反应。然而，加入四氢呋喃（THF）会引发去质子化反应，从而得到单体Ae - 锗化物配合物[(BDI)Ae{GePh}(THF)]，这两种配合物均已通过结构表征。虽然当Ae = Ca时这个过程很容易进行，但类似的基于镁的反应需要加热到>100°C，在此条件下，由于THF开环以及生成碱土金属锗基 - C - 端正丁氧基化物[(BDI)Mg{μ - O(CH₂)GePh}]，锗化物的形成变得复杂。[(BDI)Ca{GePh}(THF)]与N,N'-二异丙基碳二亚胺和二苯甲酮反应分别生成锗基脒化物和锗基醇盐衍生物[(BDI)Ca{(i - PrN)CGePh}(THF)]和[(BDI)Ca{OC(GePh)Ph}(THF)]，这表明它在亲核加成反应中作为[PhGe]阴离子的明确且可溶来源的潜力。
