两种异构的自组装硫代砷酸盐大环化合物的合成与表征

Synthesis and characterization of two isomeric, self-assembled arsenic-thiolate macrocycles.

作者信息

Vickaryous W Jake, Healey Elisabeth Rather, Berryman Orion B, Johnson Darren W

机构信息

Department of Chemistry, 1253, University of Oregon, Eugene, Oregon 97403, USA.

出版信息

Inorg Chem. 2005 Dec 12;44(25):9247-52. doi: 10.1021/ic050954w.

DOI:10.1021/ic050954w

PMID:16323906

Abstract

The use of labile As-S bond formation in the self-assembly of discrete supramolecular structures is extended. Macrocyclic structures of chemical formula As2L2Cl2 (H2L=alpha,alpha'-dimercapto-p-xylene) were prepared and characterized. Diastereomeric syn and anti isomers of these macrocycles were selectively crystallized and characterized in the solid state using single-crystal X-ray diffraction. Both the syn and anti macrocycles show close contacts between the arsenic(III) ions and the aromatic carbons, consistent with intramolecular arsenic-pi interactions. The dynamic behavior of the isomers in solution is also investigated. anti-As2L2Cl2.AsCl3 crystallizes in monoclinic space group P2(1)/c (No. 14) with a=10.6194(5) A, b=16.7780(9) A, c=8.5725(4) A, beta=100.6830(10) degrees, and Z=2. syn-As2L2Cl2 crystallizes in orthorhombic space group Pnma (No. 62) with a=10.8881(8) A, b=19.3511(14) A, c=9.9524(7) A, and Z=4.

摘要

不稳定的砷 - 硫键形成在离散超分子结构自组装中的应用得到了拓展。制备并表征了化学式为As₂L₂Cl₂（H₂L = α,α'-二巯基对二甲苯）的大环结构。这些大环的非对映体顺式和反式异构体通过单晶X射线衍射在固态下被选择性结晶并表征。顺式和反式大环都显示出砷（III）离子与芳族碳之间的紧密接触，这与分子内砷 - π相互作用一致。还研究了异构体在溶液中的动态行为。反式 - As₂L₂Cl₂·AsCl₃在单斜空间群P2(1)/c（编号14）中结晶，a = 10.6194(5) Å，b = 16.7780(9) Å，c = 8.5725(4) Å，β = 100.6830(10)°，Z = 2。顺式 - As₂L₂Cl₂在正交空间群Pnma（编号62）中结晶，a = 10.8881(8) Å，b = 19.3511(14) Å，c = 9.9524(7) Å，Z = 4。