Substituent effects on shape deformation and energies of the silicon and germanium double bond

Citation
Wc. Chen et al., Substituent effects on shape deformation and energies of the silicon and germanium double bond, ORGANOMETAL, 20(3), 2001, pp. 564-567
Citations number
42
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANOMETALLICS
ISSN journal
0276-7333 → ACNP
Volume
20
Issue
3
Year of publication
2001
Pages
564 - 567
Database
ISI
SICI code
0276-7333(20010205)20:3<564:SEOSDA>2.0.ZU;2-B
Abstract
Substituent effects on the disubstituted heavier analogues of olefin A(2)X= YH2 (X, Y = Si, Ge; A = H, CH3, NH2, OH, F, and Cl) were investigated using density functional theory (B3LYP/6-321+G*). Our theoretical findings sugge st that the strength of the rr-bond and the tendency to tl ans-bending are strongly related to the singlet-triplet energy, gap (DeltaE(st)) of the cor responding disubstituted divalent species A(2)X: Namely, as DeltaE(st) bcco nzes larger, the pi -bond is weakened, the distortion increases, and the th ermodynamic stability of the doubly bonded molecule is reduced. In this reg ard, heavier analogues of olefins with more electropositive substituents (o r more bulky groups) will give rise to less distortion and possess gl eater thermodynamic stability, making them interesting goals for synthesis and i solation.