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Pentaatomic planar tetracoordinate silicon with 14 valence electrons: A large‐scale global search of
 SiXnYmq (n + m = 4; q = 0, ±1, −2; X, Y = main group elements from H to Br)

Designing and characterizing the compounds with exotic structures and bonding that seemingly contrast the traditional chemical rules are a never‐ending goal. Although the silicon chemistry is dominated by the tetrahedral picture, many examples with the planar tetracoordinate‐Si skeletons have been discovered, among which simple species usually contain the 17/18 valence electrons. In this work, we report hitherto the most extensive structural search for the pentaatomic ptSi with 14 valence electrons, that is, SiXnYmq (n + m = 4; q = 0, ±1, −2; X, Y = main group elements from H to Br). For 129 studied systems, 50 systems have the ptSi structure as the local minimum. Promisingly, nine systems, that is, Li3SiAs2− , HSiY3 (Y = Al/Ga), Ca3SiAl−, Mg4Si2−, C2LiSi, Si3Y2 (Y = Li/Na/K), each have the global minimum ptSi. The former six systems represent the first prediction. Interestingly, in HSiY3 (Y = Al/Ga), the H‐atom is only bonded to the ptSi‐center via a localized 2c–2e σ bond. This sharply contradicts the known pentaatomic planar‐centered systems, in which the ligands are actively involved in the ligand–ligand bonding besides being bonded to the planar center. Therefore, we proposed here that to generalize the 14e‐ptSi, two strategies can be applied as (1) introducing the alkaline/alkaline‐earth elements and (2) breaking the peripheral bonding. In light of the very limited global ptSi examples, the presently designed six systems with 14e are expected to enrich the exotic ptSi chemistry and welcome future laboratory confirmation. © 2014 Wiley Periodicals, Inc.