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Quantum-chemical ab initio and time-dependent density functional theory (TD-DFT) calculations employing various basis sets were used to elucidate the spatial as well as the electronic structure of C 5 H 5 Al () and C 5 H 5 Ga ( 2 ) (ala- and galabenzene). The lowest closed shell singlet states of both compounds were found to have a non-planar structure of  C  S  symmetry with C-X-C bond angles of about 116° (MP2/6-311++G**) and 125° (CCSD/aug-cc-pVDZ). At approximately 103°, the corresponding angles of the lowest triplets are significantly smaller. The lowest triplet state of alabenzene is also non-planar ( C  S ) at the MP2 level while optimization with the CCSD and the CASPT2 method resulted in planar structures with  C  2v  symmetry. The corresponding state of galabenzene has  C  2v  symmetry at all levels of optimization. The relative stability of the lowest closed shell singlet and the lowest triplet (Δ E ( T  1 - S  0 )) state is small and its sign even strongly method-dependent. However, according to the highest levels of theory applied in this study the singlet states of both molecules are slightly lower in energy than the corresponding triplets with singlet/triplet gaps between about 0.5 and 5.8 kcal/mol in favour of the singlet states. Most of the applied methods give a slightly smaller splitting for ala- than for galabenzene. Independent of the applied method (TD-DFT/CAM-B3LYP/6-311++G(3df,3pd)//MP2/6- 311++G** or SAC-CI/6-31++G(3df,3pd)//MP2/6-311++G**), the general shape of the calculated UV/VIS spectral curves are quite similar for the lowest singlet states of ala- and galabenzene, and the same applies to the spectra of the normal modes. The calculated UV/VIS spectra of C 5 H 5 Al and C 5 H 5 Ga are featured by long wavelength bands of moderate intensity around 900 nm at the TD-DFT and between 1300 and 1500 nm at the SAC-CI level. According to both methods these bands are predominantly due to HOMO(π)→LUMO(σ*) transitions. The results of isodesmic bond separation reactions for the singlet states indicate some degree of stabilization due to delocalization in both of the title compounds. With our best values between 29 and 32 kcal/mol this stabilization appears to be only slightly less than the previously reported value for borabenzene (∼38 kcal/mol).

Quantum-Chemical Ab Initio Calculations on Ala-(C 5 H 5 Al) and Galabenzene (C 5 H 5 Ga)