Timoshkin, Alexey Y. and Bodensteiner, Michael and Sevastianova, Tatiana N. and Lisovenko, Anna S. and Davydova, Elena I. and Scheer, Manfred and Grassl, Christian and Butlak, Alina V. (2012) Do Solid-State Structures Reflect Lewis Acidity Trends of Heavier Group 13 Trihalides? Experimental and Theoretical Case Study. INORGANIC CHEMISTRY, 51 (21). pp. 11602-11611. ISSN 0020-1669, 1520-510X
Full text not available from this repository. (Request a copy)Abstract
Lewis acidity trends of aluminum and gallium halides have been considered on the basis of joint X-ray and density functional theory studies. Structures of complexes of heavier group 13 element trihalides MX3 (M = Al, Ga; X = Cl, Br, I) with monodentate nitrogen-containing donors Py, pip, and NEt3 as well as the structure of the AlCl3 center dot PPh3 adduct have been established for the first time by X-ray diffraction studies. Extensive theoretical studies (B3LYP/TZVP level of theory) of structurally characterized complexes between MX3 and nitrogen-, phosphorus-, arsenic-, and oxygen-containing donor ligands have allowed us to establish the Lewis acidity trends Al > Ga, Cl approximate to Br > I. Analysis of the experimental and theoretical results points out that the solid state masks the Lewis acidity trend of aluminum halides. The difference in the Al-N bond distances between AlCl3 center dot D and AlBr3 center dot D complexes in the gas phase is small, while in the condensed phase, shorter Al-N distances for AlBr3 center dot D complexes are observed with 9-fluorenone, mdta, and NEt3 donors. The model based on intermolecular (H center dot center dot center dot X) interactions in solid adducts is proposed to explain this phenomenon. Thus, the donor-acceptor bond distance in the solid complexes cannot always be used as a criterion of Lewis acidity.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | COVALENT METAL-HALIDES; RAY CRYSTAL-STRUCTURES; QUANTITATIVE ASPECTS; SUBSTITUTED ANILINES; ELECTRON-DIFFRACTION; ALUMINUM TRICHLORIDE; GALLIUM TRICHLORIDE; ADDITION-COMPOUNDS; ALCL3-PYRIDINE ADDUCTS; COORDINATION-COMPOUNDS; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 04 May 2020 08:26 |
| Last Modified: | 04 May 2020 08:26 |
| URI: | https://pred.uni-regensburg.de/id/eprint/17817 |
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