Heterotopic assemblage of two different disk-shaped ligands through trinuclear silver(I) complexation: Ligand exchange-driven molecular motion
Heterotopic assemblage of two different disk-shaped ligands through trinuclear silver(I) complexation: Ligand exchange-driven molecular motion
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DOI：
10.1021/ja036388q
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发表时间：
2004-02-04
影响因子：
15
通讯作者：
Shionoya, M
中科院分区：
文献类型：
--
作者：
Hiraoka, S;Shiro, M;Shionoya, M
Ag(3)1.2是由三（噻唑基）和六（噻唑基）盘形配体1和2在三个Ag+离子的辅助下形成的三明治状异位Ag+配合物。对其络合行为的变温H-1核磁共振研究表明，相邻的2的两个噻唑基氮给体之间的金属配体交换在三个Ag+中心一致发生。δ tah（双匕首）和δ tas（双匕首）的交换过程分别为50.5 kJ mol（-1）和-26.7 J mol(-1) K-1，其在298 K时的能垒估计为58.5 kJ mol（-1）。每个协调的金属配体交换导致两个圆盘状配体之间的分子内60度旋转运动(（P)可逆箭头(M)转换）。
The sandwich-shaped heterotopic trinuclear Ag+ complex Ag(3)1.2 was exclusively formed from two different tris(thiazolyl) and hexa(thiazolyl) disk-shaped ligands, 1 and 2, with the aid of three Ag+ ions. The variable-temperature H-1 NMR study on its complexation behavior revealed that metal-ligand exchanges between the two neighboring thiazolyl nitrogen donors of 2 take place at the three Ag+ centers in concert. DeltaH(double dagger) and DeltaS(double dagger) for the exchange process were calculated to be 50.5 kJ mol(-1) and -26.7 J mol(-1) K-1, respectively, and its energy barrier at 298 K was estimated to be 58.5 kJ mol(-1). Each concerted metal-ligand exchange leads to an intramolecular 60degrees-rotational motion ((P)reversible arrow(M) conversion) between the two disk-shaped ligands.