Hypercoordination in triphenyl oxinates of the group 14 elements

The triphenyl oxinates of the group 14 elements (M = Si, Ge, Sn, and Pb) contain the 8-hydroxyquinoline ligand (HOx), which can function in either a bidentate or monodentate fashion. The compounds Ph3MOx were prepared by reaction of the triphenylmetal chloride with HOx in the presence of an HCl scavenger triethylamine or, sodium acetate, and in the case of lead, with the sodium salt of 8-hydroxyquinoline. The interaction of the nitrogen with the central atom was studied through the use of the NMR chemical shifts of the central metal atom and the 15N atom of the ligand. The chemical shifts of the central metal provided evidence that the triphenylgermanium and silicon oxinates are uncoordinated while the triphenyltin and lead oxinates are five-coordinate. These conclusions are confirmed by molecular modeling, 15N chemical shifts and the metal–13C one bond coupling constants at the ipso carbon. The NMR data provides evidence that the strength of the interaction of the nitrogen with the metal increases from silicon and germanium to lead. Two peaks in the 5-coordinate region of the 207Pb NMR spectra can be rationalized with the postulate that strong interaction with lead produces two geometrical isomers. Two peaks were also present in the 5-coordinate region of the 119Sn NMR spectra at low temperatures indicating a rapid exchange between the two geometrical isomers at room temperature.

Graphical abstractThe Group 14 triphenyl oxinates show 5-coordinate structures for tin and lead with two fluxional geometric isomers. The silicon and germanium analogs are 4-coordinate. These conclusions, derived from multinuclear NMR studies, are corroborated by DFT modeling.Figure optionsDownload full-size imageDownload as PowerPoint slide