Group 14 structural variations: perhalo derivatives of the “dimetallenes”: dicarbenes, disilenes, digermenes, distannenes, and diplumbenes

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Trends in the structural variations of all perhalo derivatives of dicarbenes and their Group 14 analogues have been studied. This included all M2X4 molecules, where M = C, Si, Ge, Sn, or Pb, and X = F, Cl, Br, or I. Mapping the potential energy surface of all molecules has uncovered several isomers. The stability of these isomers depends on both the Group 14 atoms and the halogen ligands. Several isomers were found stable; the ones that are global minima include (with their symmetries and an example in parenthesis): the typical ethene structure X2M=MX2 (D2h, F2C=CF2), an X3M–MX structure (CS, F3Si–SiF, a trifluorosilyl–silylene), another X3M–MX structure (C1, Cl3Si–SiCl), one more X3M–MX structure with a single halogen bridge (C1, I2Si–μI–SiI), a trans double halogen bridged structure (D2h, FSn–μF2–SnF), and another trans double-bridged structure with puckered ring (CS, IPb–μI2–PbI). Some of the other structures that are stable but are not the global minima include: a trans-bent structure X2M–MX2 (C2h, all X2Si–SiX2), cis double-bridged structure (C2v with planar ring, FPb–μF2–PbF, or with puckered ring, C2v, IGe–μI2–GeI), and even a square bipyramidal structure (D4h, Sn–μF4–Sn). The energy differences between some of the structures are small and the application of another computational method and using a different basis set might alter their relative stabilities. Reasons for the difference in the stabilities of isomers have been discussed.