Umbrella-like inversion of pyramidalized amines proceed through a planar transition state (TS). Stabilization of the TS through N(lone-pair) -> sigma*(C-C) "negative hyperconjugation" in diamino-o-carborane (1) causes rapid inversion in the amine, which results in the observation of a planarized -NH2 from the X-ray crystal structure. This proceeds through quantum mechanical tunneling across the small and narrow barrier (low pyramidalization). Tuning this secondary orbital (donor-acceptor) interaction for various derivatives of 1 and diamino-ododecahedron (2) provides a rational approach toward increasing d(C-C) to as large as 2.001, 2.011, and 1.807 angstrom for 1b (amino oxide-o-carborane), 1i (di-N,N-dimethylamino-o-carborane), and 2g (di-N,N-diisopropylamino-o-dodecahedron), respectively.