STABILITIES AND STRUCTURES OF HALOGENATED DIALANES

被引:10
作者
BOCK, CW
TRACHTMAN, M
MAINS, GJ
机构
[1] AMER RES INST, UPPER DARBY, PA 19082 USA
[2] OKLAHOMA STATE UNIV, DEPT CHEM, STILLWATER, OK 74078 USA
关键词
D O I
10.1021/j100113a014
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The ab initio structures and energies of all the isomers of Al2HnX6-n (n = 0-6, X = F, Cl) have been calculated at the HF/6-31G* level. Correlation has been included at the MP2/6-31G*//HF/6-31G* level in all cases and at the MP4SDTQ/6-31G*//RHF/6-31G* and MP2/6-31G*//MP2/6-31G* levels in a few cases. Ab initio structures and energies are also presented for selected chlorofluorodialanes, Al2HnClmFp (n + m + p = 6). Dissociation energies, including zero-point corrections, are presented for all molecules at the MP2/6-31G*//RHF/6-31G* level. Acid-base interaction parameters deduced from the computed dissociation energies of 28 molecules are shown to be sufficient to predict the computed dissociation energies of 32 other chlorodialanes, fluorodialanes, and selected chlorofluorodialanes with an root mean square error of 1.2 kcal/mol. The applicability of these Lewis acid/base interaction parameters in assigning Lewis acid strengths and Lewis base strengths is discussed, and the utility of describing the bonding in terms of three-center two-electron bonds is considered.
引用
收藏
页码:2546 / 2554
页数:9
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