Laglera Gándara, Carlos J.Ríos Moreno, PabloFernández de Córdova, Francisco JoséBarturen, MarinaFernández, IsraelConejero, Salvador2024-08-302024-08-302022Laglera Gándara, C.J., Ríos Moreno, P., Fernández de Córdova, F.J., Barturen, M., Fernández, I. y Conejero, S. (2022). σ‑GeH and Germyl Cationic Pt(II) Complexes. Inorganic Chemistry, 61 (51), 20848-20859. https://doi.org/10.1021/acs.inorgchem.2c03186.1520-510X0020-1669https://hdl.handle.net/11441/162136The low electron count Pt(II) complexes [Pt(NHC′)(NHC)]- [BArF] (where NHC is a N-heterocyclic carbene ligand and NHC′ its metalated form) react with tertiary hydrogermanes HGeR3 at room temperature to generate the 14-electron platinum(II) germyl derivatives [Pt(GeR3)(NHC)2][BArF]. Low-temperature NMR studies allowed us to detect and characterize spectroscopically some of the σ-GeH intermediates [Pt(η2-HGeR3)(NHC′)(NHC)][BArF] that evolve into the platinum-germyl species. One of these compounds has been characterized by X-ray diffraction studies, and the interaction of the H−Ge bond with the platinum center has been analyzed in detail by computational methods, which suggest that the main contribution is the donation of the H−Ge to a σ*(Pt−C) orbital, but backdonation from the platinum to the σ*(Ge−H) orbital is significant. Primary and secondary hydrogermanes also produce the corresponding platinum-germyl complexes, a result that contrasts with the reactivity observed with primary silanes, in which carbon−silicon bond-forming reactions have been reported. According to density functional theory calculations, the formation of Pt−Ge/C−H bonds is both kinetically and thermodynamically preferred over the competitive reaction pathway leading to Pt−H/C−Ge bonds.application/pdf12 p.engAtribución 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/articleinfo:eu-repo/semantics/openAccesshttps://doi.org/10.1021/acs.inorgchem.2c03186