The Reactivity of Phosphagermaallene Mes*P═C═Ge(<i>t</i>-Bu)Tip toward Aldehydes and Ketones: an Experimental and Theoretical Study
作者:F. Ouhsaine、E. André、J. M. Sotiropoulos、J. Escudié、H. Ranaivonjatovo、H. Gornitzka、N. Saffon、K. Miqueu、M. Lazraq
DOI:10.1021/om100233y
日期:2010.6.14
Mes*P═C═Ge(t-Bu)Tip 1 (Tip = 2,4,6-triisopropylphenyl, Mes* = 2,4,6-tri-tert-butylphenyl) has been obtained by an improved synthesis in relation to the previously reported preparation starting from t-BuGeCl3. Very short Ge═C (1.761(2) Å) and P═C (1.625(2) Å) double bond lengths, trigonal planar geometry around the Ge atom, and GeCP bond angle of 166.57° are indicative of an heteroallenic structure for 1. Its reactions
Phosphagermaallene的Mes *P═C═Ge(吨-Bu)提示1(提示= 2,4,6-三异丙基,MES * = 2,4,6-三-叔丁基苯基)已通过相对于一种改进的合成法得到的到先前报道的从t- BuGeCl 3开始的制备方法。非常短的Ge═C(1.761(2)Å)和P═C(1.625(2)Å)双键长度,Ge原子周围的三角平面几何形状以及166.57°的GeCP键角表明1的杂亚烯基结构。它与巴豆醛和肉桂醛的反应通过Ge═C和C═O双键之间的[2 + 2]环加成反应生成1-oxa-2-germacyclobutanes。与甲基乙烯基酮一起,观察到Ge═C和O═C-C═C部分之间的[2 + 4]环加成反应和烯反应,导致生成1-oxa-2-germacyclohex-5-ene和胚芽(丁二烯基)醚。与苯乙酮一起,发生烯反应以仅提供胚芽(乙烯基)醚。已经进行了DFT计算以解释观察到的区域化学。