Institut für Chemie: Metalorganics and Inorganic Materials, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany.
Chemistry. 2011 Apr 18;17(17):4890-5. doi: 10.1002/chem.201003409. Epub 2011 Mar 8.
The first isolable pyridine-stabilized germanone has been prepared and its reactivity toward trimethylaluminum has been investigated. The germanone adduct results from a stepwise conversion that starts from 4-dimethylaminopyridine (DMAP) and the ylide-like N-heterocyclic germylene LGe: (L=CH{(C=CH(2))(CMeN(aryl)}, aryl=2,6-iPr(2)C(6)H(3)) (1) at room temperature, and gives the corresponding germylene-pyridine adduct L(DMAP)Ge: (2) in 91% yield. The latter reacts with N(2) O at room temperature to form the desired germanone complex L(DMAP)Ge=O (3) in 73% yield. The Ge-O distance of 1.646(2) Å in 3 is the shortest hitherto reported for a Ge=O species. The reaction of 3 with trimethylaluminum leads solely to the addition product LGe(Me)O[Al(DMAP)Me(2)] (4). The latter results from insertion of the Ge=O subunit into an Al-Me bond of AlMe(3) and concomitant migration of the DMAP ligand from germanium to the aluminum atom. Compounds 2-4 have been fully characterized by analytical and spectroscopic methods. Their molecular structures have been established by single-crystal X-ray crystallographic analysis.
首例可分离的吡啶稳定的锗烯已经被制备出来，并对其与三甲基铝的反应性进行了研究。该锗烯加合物是由逐步转化而来的，起始于 4-二甲氨基吡啶（DMAP）和类叶立德的 N-杂环锗烯 LGe：（L=CH{(C=CH(2))(CMeN(芳基)}，芳基=2,6-iPr(2)C(6)H(3)）（1），在室温下，得到相应的锗烯-吡啶加合物 L(DMAP)Ge：（2），产率为 91%。后者在室温下与 N(2)O 反应，以 73%的产率生成所需的锗烯配合物 L(DMAP)Ge=O（3）。3 中 Ge-O 距离为 1.646(2)Å，是迄今为止报道的最短的 Ge=O 物种。3 与三甲基铝的反应仅导致加合物 LGe(Me)O[Al(DMAP)Me(2)]（4）的生成。后者是由于 Ge=O 亚基插入 AlMe(3)的 Al-Me 键中，同时 DMAP 配体从锗迁移到铝原子。化合物 2-4 已通过分析和光谱方法进行了充分的表征。其分子结构已通过单晶 X 射线晶体学分析确定。
