Group 14 structural variations: Perhalo derivatives of the "dimetallenes": Dicarbenes, disilenes, digermenes, distannenes, and diplumbenes

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Abstract

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.

Original languageEnglish
Pages (from-to)837-850
Number of pages14
JournalStructural Chemistry
Volume24
Issue number3
DOIs
Publication statusPublished - Jun 2013

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Isomers
Halogens
isomers
halogens
Derivatives
rings
Potential energy surfaces
Molecules
Computational methods
molecules
potential energy
analogs
Ligands
trends
Atoms
ligands
symmetry
atoms
energy

Keywords

  • Dicarbene
  • Digermene
  • Diplumbene
  • Disilene
  • Distannene
  • Group 14
  • Metal dihalide dimer
  • Structural trends
  • Tetrahalo-dicarbene

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

@article{4f315df41a8740b9b93499335ffbd2ac,
title = "Group 14 structural variations: Perhalo derivatives of the {"}dimetallenes{"}: Dicarbenes, disilenes, digermenes, distannenes, and diplumbenes",
abstract = "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.",
keywords = "Dicarbene, Digermene, Diplumbene, Disilene, Distannene, Group 14, Metal dihalide dimer, Structural trends, Tetrahalo-dicarbene",
author = "Z. Varga and M. Hargittai",
year = "2013",
month = "6",
doi = "10.1007/s11224-012-0194-9",
language = "English",
volume = "24",
pages = "837--850",
journal = "Structural Chemistry",
issn = "1040-0400",
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TY - JOUR

T1 - Group 14 structural variations

T2 - Perhalo derivatives of the "dimetallenes": Dicarbenes, disilenes, digermenes, distannenes, and diplumbenes

AU - Varga, Z.

AU - Hargittai, M.

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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