THE STRUCTURE AND STABILITY OF THE 10-F-2 TRIFLUORIDE ION, A COMPOUND OF A HYPERVALENT 1ST ROW ELEMENT
THE STRUCTURE AND STABILITY OF THE 10-F-2 TRIFLUORIDE ION, A COMPOUND OF A HYPERVALENT 1ST ROW ELEMENT
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DOI：
10.1021/ja00308a032
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发表时间：
1985-01-01
影响因子：
15
通讯作者：
MARTIN, JC
中科院分区：
文献类型：
--
作者：
CAHILL, PA;DYKSTRA, CE;MARTIN, JC
用从头算电子结构计算方法研究了三氟离子的结构。经计算，其相对于F1和F2稳定约11 kcal/mol。虽然这表示F1与F2形成F3-的相对弱的键合，但在形成DnhF 3-时，F2键的0.3-π延长（从1.41至1.70 π）证明了显著的相互作用。FF键距的这种延长降低了F2的氟的未共享电子对的排斥型相互作用，并且据推测，这提供了对dichloratrifluoride离子的主要稳定影响。计算出的质心平衡结构，沿着计算出的振动常数，一般是一致的矩阵隔离实验报道的奥尔特和安德鲁斯。讨论了这种独特的主群超价分子的成键性质。
Well correlated ab initio electornicstructure calculations have been used to investigate the structure of the trifluoride ion. It is calculated to be stable with respect to F" and F2 by about 11 kcal/mol. While this represents a relatively weak bonding of F^ to F2 to form F3~, a significant interaction is evidenced by a 0.3-Á lengthening of the F2 bond (from 1.41 to 1.70 Á) upon forming the D „h F3~. This lengthening of the FF bond distance decreases the repulsive-type interactions of the unshared electron pairs of the fluorines of F2, and it is postulated that this provides a major stabilizing influence on the symmetricaltrifluoride ion. The calculated centrosymmetricequilibrium structure, along with the calculated vibrational constants, is generally consistent with matrix isolation experiments reported earlier by Ault and Andrews. The nature of the bonding in this unique main group hypervalent molecule is discussed.