TY - JOUR
T1 - Group 14 structural variations
T2 - Perhalo derivatives of the "dimetallenes": Dicarbenes, disilenes, digermenes, distannenes, and diplumbenes
AU - Varga, Zoltán
AU - Hargittai, Magdolna
PY - 2013/6
Y1 - 2013/6
N2 - 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 (D 2h, F2C=CF2), an X3M-MX structure (C S, F3Si-SiF, a trifluorosilyl-silylene), another X 3M-MX structure (C 1, Cl3Si-SiCl), one more X3M-MX structure with a single halogen bridge (C 1, I 2Si-μI-SiI), a trans double halogen bridged structure (D 2h, FSn-μF2-SnF), and another trans double-bridged structure with puckered ring (C S, IPb-μI2-PbI). Some of the other structures that are stable but are not the global minima include: a trans-bent structure X2M-MX2 (C 2h, all X 2Si-SiX2), cis double-bridged structure (C 2v with planar ring, FPb-μF2-PbF, or with puckered ring, C 2v, IGe-μI2-GeI), and even a square bipyramidal structure (D 4h, 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.
AB - 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 (D 2h, F2C=CF2), an X3M-MX structure (C S, F3Si-SiF, a trifluorosilyl-silylene), another X 3M-MX structure (C 1, Cl3Si-SiCl), one more X3M-MX structure with a single halogen bridge (C 1, I 2Si-μI-SiI), a trans double halogen bridged structure (D 2h, FSn-μF2-SnF), and another trans double-bridged structure with puckered ring (C S, IPb-μI2-PbI). Some of the other structures that are stable but are not the global minima include: a trans-bent structure X2M-MX2 (C 2h, all X 2Si-SiX2), cis double-bridged structure (C 2v with planar ring, FPb-μF2-PbF, or with puckered ring, C 2v, IGe-μI2-GeI), and even a square bipyramidal structure (D 4h, 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.
KW - Dicarbene
KW - Digermene
KW - Diplumbene
KW - Disilene
KW - Distannene
KW - Group 14
KW - Metal dihalide dimer
KW - Structural trends
KW - Tetrahalo-dicarbene
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U2 - 10.1007/s11224-012-0194-9
DO - 10.1007/s11224-012-0194-9
M3 - Article
AN - SCOPUS:84879094044
SN - 1040-0400
VL - 24
SP - 837
EP - 850
JO - Structural Chemistry
JF - Structural Chemistry
IS - 3
ER -