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Chlorogallanes (GaClH2, GaCl2H, and GaCl3) and their dimer isomers

Duke, Brian J., Hamilton, Tracy P. and Schaefer III, Henry F. (1991). Chlorogallanes (GaClH2, GaCl2H, and GaCl3) and their dimer isomers. Inorganic Chemistry,30(22):4225-4229.

Document type: Journal Article
Citation counts: Scopus Citation Count Cited 17 times in Scopus Article | Citations

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Title Chlorogallanes (GaClH2, GaCl2H, and GaCl3) and their dimer isomers
Author Duke, Brian J.
Hamilton, Tracy P.
Schaefer III, Henry F.
Journal Name Inorganic Chemistry
Publication Date 1991
Volume Number 30
Issue Number 22
ISSN 0020-1669   (check CDU catalogue open catalogue search in new window)
Scopus ID 2-s2.0-0000683650
Start Page 4225
End Page 4229
Total Pages 5
Place of Publication United States of America
Publisher American Chemical Society
Field of Research 0302 - Inorganic Chemistry
Abstract The dimers of the three chlorides of gallium(III) have been studied by using ab initio quantum-mechanical methods at high levels of theory for these relatively large molecules. The problem of accurately predicting the geometry of the bridge region is investigated. Large basis sets (including f functions) and electron correlation are required to obtain the Ga-Clb distance correctly (b denotes bridging). Theoretical bond angles converge much more quickly with respect to level of theory, leading us to suggest that the experimental Ga-Clb-Ga angle of 87.2° for Ga2Cl2H4 be revised slightly upward to 90°. The H-Ga-H angle is predicted to be 132°. The geometry and energy of all possible isomers of the monochloro- and dichlorogallane dimers are also reported, as well as those for Ga2Cl6. Agreement between theory and experiment for Ga2Cl6 is significantly better than for Ga2Cl2H4. For each Cl on a bridging site, the dimerization energy (relative to an analogous molecule with a H at that site) is increased by 6-8 kcal mol-1, and for each terminally bonded Cl the dimerization energy is decreased by 1-2 kcal mol-1 relative to the analogous molecule with a H bonded at that position. Harmonic vibrational frequencies for the monochlorogallane dimer are predicted and compare well with the experimental infrared and Raman fundamentals.
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Created: Fri, 29 Aug 2014, 20:26:48 CST by Anthony Hornby