The phenyltetrel pyridine-2-olates PhE(pyO)3 (E = Si, Ge, Sn; pyO = pyridine-2-olate) were synthesized from the respective chlorides PhECl3 and 2-hydroxypyridine (2-pyridone) with the aid of a sacrificial base (triethylamine). Their solid-state structures were determined by single-crystal X-ray diffraction. PhSi(pyO)3 exhibits a three-fold capped tetrahedral Si coordination sphere ([4+3]-coordination, Si···N separations ca. 3.0 Å), in accordance with structures of previously reported silicon

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... idine-2-olates. PhGe(pyO)3 adopts a related [4+3]-coordination mode, which differs in terms of the tetrahedral faces capped by the pyridine N atoms. Additionally, shorter Ge···N separations (2.8–2.9 Å) indicate a trend toward tetrel hypercoordination. PhSn(pyO)3 features heptacoordinate tin within a pentagonal bipyramidal Sn coordination sphere (Sn···N separations 2.2–2.4 Å). For the Si and Sn compounds, 29Si and 119Sn NMR spectroscopy indicates retention of their tetrel coordination number in chloroform solution.