A novel triplet germylene F3C{single bond}over(Ge, ̈){single bond}Ge{triple bond, long}Ge{single bond}H at theoretical levels

M. Z. Kassaee, F. Buazar, S. Soleimani-Amiri, M. R. Momeni

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

F3C{single bond}over(Ge, ̈){single bond}Ge{triple bond, long}Ge{single bond}H, with two unpaired electrons, is the only triplet (t) ground state germylene found among 30 divalent species, with XHGe3 formula, at six reasonably high ab initio and DFT levels (X = H, NH2, SiH3, and CF3). Its corresponding singlet (s) appears at a higher energy while showing a negative force constant. The crossing angle (F{cyrillic}) between the above s and t states is 90°. Replacement of CF3 with H and NH2 increases F{cyrillic} to 120° and 160°, respectively. No crossing of the s and t states occurs for H3Si{single bond}Ge{single bond}Ge{triple bond, long}Ge{single bond}H, whose s state is its global minimum. Having X directly attached to the divalent germylene in X{single bond}Ge{single bond}Ge{triple bond, long}Ge{single bond}H, increases the X effects on ΔEs-t,X compared to the isomeric species: 3-X-1,2,3-trigermapropargylene, 3-X-1,2,3-trigermavinylidene and 2-X-1,2,3-trigermacyclopropenylidene, respectively. Nonetheless, the latter cyclic divalent species appear relatively more stable with the highest LUMO-HOMO energy gaps, while their NICS calculations show their aromatic character change as a function of X (SiH3 > H > CF3 > NH2). Finally, the global minimum among the 30 isomeric XHGe3 is found to be SiH3 substituted singlet trigermacyclopropenylidene.

Original languageEnglish (US)
Pages (from-to)46-53
Number of pages8
JournalJournal of Molecular Structure: THEOCHEM
Volume899
Issue number1-3
DOIs
StatePublished - Apr 15 2009

Bibliographical note

Funding Information:
This research was supported by Iranian National Science Foundation, Grant No.: 85053/17.

Keywords

  • CFHGe
  • Germylene
  • HGe
  • HNGe
  • HSiGe

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