Analysis of the supramolecular structures of Sb(III) and Sb(V) catecholate complexes from the viewpoint of ligand solid angles

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• 作者：Georgy K. Fukin ; Ilia A. Guzei ; Evgenii V. Baranov and Georgy A. Domrachev
• 关键词：Catecholate complexes of Sb(III) and Sb(V) ; Supramolecular structure ; Steric saturation of the metal coordination environment ; The ligand solid angle approach
• 刊名：Structural Chemistry
• 出版年：2009
• 出版时间：August, 2009
• 年：2009
• 卷：20
• 期：4
• 页码：643-654
• 全文大小：509.1 KB

文摘

The ligand solid angle approach has been successfully applied to the analysis of the catecholate complexes of Sb(III) and Sb(V). The Sb(III) complexes possess an electron lone pair that influences their molecular structure but does not behave as a classic “ligand” when intermolecular interactions are concerned. The Sb(III) complexes in solid state form numerous intermolecular interactions that effectively increase metal shielding, and herein we analyze the effects of the lone pair of electrons on the complex coordination geometry. In the five-coordinate R₃CatSb(V) complexes (Cat = catecholate ligand, R = Ph, Me, Cl) the metal is shielded by 87(3) % and multiple intermolecular contacts are observed. The central metal in the six-coordinate antimony(V) complexes R₃CatSb(V) ¡¤ L is shielded to the extent of 89(2) % and no strong attractive intermolecular interactions are detected in solid state. Thus, the metal shielding in excess of 85 % is required to prevent complex dimerization or additional ligation of the central atom by a nucleophile.