Integrating the Substituent Effect into the Wade-Mingos Rules for Dicarboranes.

ABSTRACT: This work revisits the Wade-Mingos (W-M) rules in carborane chemistry by showing that substituent effects, rather than skeletal electron pairs alone, determine ground-state architectures. We performed high-throughput computational analysis of 74613 six-vertex dicarboranes (C₂B₄R₆), using the newly proposed Seed and Mortise-Tenon model, achieving a prediction accuracy of 92.8%. Through this analysis, we derived a simple substituent-counting rule (P = n_M + 1.1n_H) that incorporates substituent electronegativity via connected-atom electronegativity (CAEN) to predict energetic stability. According to this rule, the previously underestimated trigonal-bipyramidal isomer emerges as the global ground state in 89.1% of the cases, whereas the W-M

SUBMITTER: Wang SS 

PROVIDER: S-EPMC12723461 | biostudies-literature | 2025 Dec

REPOSITORIES: biostudies-literature