Disilanes with Pentacoordinate Si Atoms by Carbon Dioxide Insertion into Aminodisilanes: Syntheses, Molecular Structures, and Dynamic Behavior

[Image: see text] The insertion of carbon dioxide into the Si–N bonds of aminodisilanes ((RR′N)(n)Me(3–n)Si)(2) affords carbamoyloxydisilanes ((RR′NC(O)O)(n)Me(3–n)Si)(2). Some of the obtained insertion products feature pentacoordinate silicon atoms in the solid state and in solution, with two carbamoyloxy moieties bridging the Si–Si bond. The aminodisilanes and their insertion products were extensively analyzed, including single-crystal X-ray structure analyses. The temperature dependence of the higher coordination was investigated using variable temperature NMR experiments.