Journal article

Authors list: Xie, Y; Schreiner, PR; Schaefer, HF; Li, XW; Robinson, GH

Publication year: 1996

Pages: 10635-10639

Journal: Journal of the American Chemical Society

Volume number: 118

Issue number: 43

DOI Link: https://doi.org/10.1021/ja9616701

Publisher: American Chemical Society

Abstract: 

Ab initio quantum mechanical methods were applied to examine M₂(GaH)₃ (M = Li, Na, K) compounds, which are models for the newly synthesized class of Ga₃ three-membered-ring cyclogallene compounds. Basis sets of triple-ζ plus double polarization augmented with diffuse functions (TZ2P+diffuse) quality were employed at the self-consistent field (SCF) and density functional theory (B3LYP) levels of theory. Computed equilibrium geometries, harmonic vibrational frequencies, and chemical shifts are reported. The experimental (X-ray) structures of cyclogallenes are in close agreement with theory. While Na₂(GaH)₃ possesses C₃ symmetry (the deviation from C3h symmetry is very small), the remaining two compounds are C_3h symmetric. The parent neutral three-membered-ring structure (GaH)₃ is not stable as the imaginary vibrational frequencies of (GaH)₃ lead to Ga−Ga bond breaking. Upfield changes in the chemical shifts for the alkali metal atoms over and under the ring plane are taken as strong evidence for ring currents in the cyclogallene moiety. This finding and the large negative nucleus independent chemical shifts (NICS) clearly support the proposed aromatic character of the title compounds.

Harvard Citation style: Xie, Y., Schreiner, P., Schaefer, H., Li, X. and Robinson, G. (1996) Are Cyclogallenes [M2(GaH)3] (M = Li, Na, K) Aromatic?, Journal of the American Chemical Society, 118(43), pp. 10635-10639. https://doi.org/10.1021/ja9616701

APA Citation style: Xie, Y., Schreiner, P., Schaefer, H., Li, X., & Robinson, G. (1996). Are Cyclogallenes [M2(GaH)3] (M = Li, Na, K) Aromatic?. Journal of the American Chemical Society. 118(43), 10635-10639. https://doi.org/10.1021/ja9616701