CAl3X (X = B/Al/Ga/In/Tl) with 16 valence electrons: can planar tetracoordinate carbon be stable?

As a perpetual chemical curiosity, planar tetracoordinate carbon (ptC) that violates the traditional tetrahedral carbon (thC) has made enormous achievements. In particular, the 18-valence-electron (18ve) counting rule has been found to be very effective in predicting ptC structures, as in CX42− (X = Al/Ga/In/Tl). By contrast, the corresponding neutral CX4 with 16ve each takes the thC form like methane. Herein, we report a mono-substituted neutral 16ve-CAl3X (X = Al/Ga/In/Tl). Our theoretical results showed that the competition between thC and ptC can be well tuned upon variation of X, and for X = In and Tl, the ptC structure becomes isoenergetic to and even more stable than thC, respectively. Thus, a low-lying ptC can be achieved in the 16ve-CAl3X set without acquiring additional electrons. This unintuitive result can be ascribed to the increased energetic preference of the ionic sub-structure [CAl3−]X+ from X = Al to Tl. We thus predict the first penta-atomic ptC species with 16ve, and the ionic strategy presented in this work is expected to promote novel designs of ptC molecules.