Mono-silicon isoelectronic replacement in CAl4 : van't hoff/le bel carbon or not?

Abstract

In cluster studies, the isoelectronic replacement strategy has been successfully used to introduce new elements into a known structure while maintaining the desired topology. The well-known penta-atomic 18 valence electron (ve) species $C{\mathrm{Al}}_4^{2-}$ and its Al^- /Si or Al/Si⁺ isoelectronically replaced clusters CAl₃ Si^- , CAl₂ Si₂ , $C{\text{AlSi}}_3^{-}$ , and $C{\mathrm{Si}}_4^{2+}$ , all possess the same anti-van't Hoff/Le Bel skeletons, that is, nontraditional planar tetracoordinate carbon (ptC) structure. In this article, however, we found that such isoelectronic replacement between Si and Al does not work for the 16ve-CAl₄ with the traditional van't Hoff/Le Bel tetrahedral carbon (thC) and its isoelectronic derivatives CAl₃ X (X = Ga/In/Tl). At the level of CCSD(T)/def2-QZVP//B3LYP/def2-QZVP, none of the global minima of the 16ve mono-Si-containing clusters CAl₂ SiX⁺ (X = Al/Ga/In/Tl) maintains thC as the parent CAl₄ does. Instead, X = Al/Ga globally favors an unusual ptC structure that has one long C─X distance yet with significant bond index value, and X = In/Tl prefers the planar tricoordinate carbon. The frustrated formation of thC in these clusters is ascribed to the CSi bonding that prefers a planar fashion. Inclusion of chloride ion would further stabilize the ptC of CAl₂ SiAl⁺ and CAl₂ SiGa⁺ . The unexpectedly disclosed CAl₂ SiAl⁺ and CAl₂ SiGa⁺ represent the first type of 16ve-cationic ptCs with multiple bonds. © 2019 Wiley Periodicals, Inc.

Keywords: 16 valence electron; isoelectronic replacement; planar tetracoordinate carbon (ptC); planar tricoordinate carbon (p3C); tetrahedral carbon (thC); theoretical computation.