Université de Toulouse, UPS, LHFA, 118 Route de Narbonne, F-31062 Toulouse, France.
Inorg Chem. 2012 Nov 5;51(21):11716-21. doi: 10.1021/ic3016194. Epub 2012 Oct 22.
The first monogermylenerhodium complexes stabilized by bulky amidinato ligands on the divalent germanium center have been synthesized and characterized by NMR spectroscopy and X-ray crystallography. Their stability strongly depends on the steric hindrance of the amidinato ligand. With trimethysilyl groups on the nitrogen atoms of the amidinato ligand, only the germylene oxide rhodium complex could be obtained; by contrast, with t-Bu groups, the germylenerhodium complex was isolated. In both cases, the formation of amidinatorhodium complexes was observed. The donating ability of the germylene ligand has been assessed from the CO stretching frequency of the corresponding dicarbonylrhodium complex and was confirmed by density functional theory calculations.
首次合成并通过核磁共振波谱和 X 射线晶体学对二价锗中心上受大位阻酰胺配体稳定的单锗烯铑配合物进行了表征。它们的稳定性强烈依赖于酰胺配体的空间位阻。当酰胺配体的氮原子上带有三甲基硅基时，只能得到锗烯氧化物铑配合物；相比之下，当带有叔丁基时，可分离得到锗烯基铑配合物。在这两种情况下，都观察到了酰胺基铑配合物的形成。通过相应二羰基铑配合物的 CO 伸缩振动频率评估了锗烯配体的给电子能力，并通过密度泛函理论计算得到了证实。
