The substituent effect of sulfoxides in solvent extraction of palladium is investigated theoretically by using di-n-hexyl and diphenyl sulfoxide-palladium （Ⅱ） adducts as model complexes. RHF, DFT and two half-and-h...The substituent effect of sulfoxides in solvent extraction of palladium is investigated theoretically by using di-n-hexyl and diphenyl sulfoxide-palladium （Ⅱ） adducts as model complexes. RHF, DFT and two half-and-half functional （BHandHLYP and BHandH） methods have been applied in the geometry optimization, and BHandH method at the 6-31G^＊ level （Pd, 3-21G^＊） can give adequate accuracy for both free sulfoxides and their Pd （Ⅱ） complexes. As compared to diphenyl sulfoxide （DPSO）, the better affinity of di-n-hexyl sulfoxide （DHSO） towards Pd（Ⅱ） has been reasonably explained by a stronger electronic transfer, shorter Pd-S bond length and a larger binding energy in its Pd （Ⅱ） complex.展开更多
基金This work was supported by the NNSFC (20332030, 20572027), Research Grants Council of Hong Kong and SRF for ROCS, State Education Ministry
文摘The substituent effect of sulfoxides in solvent extraction of palladium is investigated theoretically by using di-n-hexyl and diphenyl sulfoxide-palladium （Ⅱ） adducts as model complexes. RHF, DFT and two half-and-half functional （BHandHLYP and BHandH） methods have been applied in the geometry optimization, and BHandH method at the 6-31G^＊ level （Pd, 3-21G^＊） can give adequate accuracy for both free sulfoxides and their Pd （Ⅱ） complexes. As compared to diphenyl sulfoxide （DPSO）, the better affinity of di-n-hexyl sulfoxide （DHSO） towards Pd（Ⅱ） has been reasonably explained by a stronger electronic transfer, shorter Pd-S bond length and a larger binding energy in its Pd （Ⅱ） complex.
