Raw Data for "A Germanium μ-Oxo Chloro Dimer En Route to a Heavier Phosgene and 1,3-Cyclodigermoxane Dications"

Treatment of 2 with H2O·B(C6F5)3 affords a Lewis acid-base stabilized germaphosgene (3), representing the first heavier analogue of carbonyl dichloride. In parallel, halide abstraction from 2 provides access to a series of 1,3-cyclodigermoxane dications (4a–e) featuring a planar Ge2O2 core.

Structural and computational analyses reveal highly polarized Ge–O bonding in both systems, with a predominantly dative O→Ge interaction in 3 and more delocalized bridging interactions in 4a–e, both lacking significant π-character. The strong donor ability of the ylide ligand is key to stabilizing the cationic germanium centers and enabling the observed reactivity. These findings establish μ-oxo germanium dimers as powerful synthetic intermediates for the construction of reactive heavier carbonyl analogues and cationic group-14 oxide frameworks, while demonstrating the tunability of Ge–O bonding from delocalized bridging to localized, partially multiple-bond character.