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tert-Butyl thiol and pyridine ligand co-protected 50-nuclei clusters: the effect of pyridines on Ag-SR bonds.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-08-07 , DOI: 10.1039/d0dt02003f
Yang-Lin Shen 1 , Jun-Ling Jin 2 , Yun-Peng Xie 1 , Xing Lu 1
Affiliation  

Constructing silver(I)–thiolate clusters from simple building blocks usually involves elusive self-assembly processes and remains a long-standing challenge. In this work, we report 6 silver(I)–thiolate clusters protected by pyridines, namely, [Ag3(tBuS)2(Py)(NO3)]n (Py = pyridine) (1), [Ag10(tBuS)6(Py)6(CF3CO2)4]·3Py (2), [Ag12(iPrS)6(Py)8(NO3)6]·2H2O (3), Ag12(iPrS)6(Py)8(CF3CO2)6 (4), Ag12(iPrS)6(4-ap)6(NO3)6 (4-ap = 4-aminopyridine) (5), and [Ag50S13(tBuS)20(Py)12]·4BF4·4Py·4CH3OH·2H2O (6). Single-crystal X-ray crystallography analysis reveals that six clusters are constructed by four types of structural blocks, including the PyAg(tBuS)2 monomer, Py2Ag2(tBuS)2 dimer, Py3Ag3(tBuS)3 trimer and (4-ap)6Ag6(iPrS)6 hexamer. Notably, cluster 6 consists of a rhombic dodecahedron S@Ag14 kernel with 12 interstitial S2− atoms encapsulated by 8 μ4-tBuS ligands, as well as six unique butterfly-like (Py)2Ag6(tBuS)2 staple motifs composed of a Py2Ag2(tBuS)2 dimer and four silver ions. Moreover, it is found that pyridine ligands have important influence on the construction of silver thiolate clusters and their Ag–SR bond lengths.

中文翻译:

叔丁基硫醇和吡啶配体共同保护50个核簇:吡啶对Ag-SR键的影响。

从简单的结构单元构建银(I)-硫醇盐簇通常涉及难以捉摸的自组装过程,并且仍然是一个长期的挑战。在这项工作中,我们报告了6个由吡啶保护的银(I)–硫醇盐簇,即[Ag 3t BuS)2(Py)(NO 3)] n(Py =吡啶)(1),[Ag 10t BuS)6(Py)6(CF 3 CO 24 ]·3Py(2),[Ag 12i PrS)6(Py)8(NO 3 6 ]·2H 2 O( 3),Ag 12 i PrS) 6(Py) 8(CF 3 CO 2 6 4),Ag 12 i PrS) 6(4-ap) 6(NO 3 6(4-ap = 4-氨基吡啶)( 5)和[Ag 50 S 13 t BuS) 20(Py) 12 ]·4BF 4 ·4Py·4CH 3 OH·2H2 O( 6)。X射线晶体学分析表明,六种簇是由四种类型的结构嵌段构成的,包括PyAg( t BuS) 2单体,Py 2 Ag 2 t BuS) 2二聚体,Py 3 Ag 3 t BuS) 3三聚体和(4-ap) 6 Ag 6 i PrS) 6六聚体。值得注意的是,簇6由菱形十二面体S @ Ag 14核组成,具有12个间隙S 2-原子,被8μ封装4 -总线-配体,以及6个独特的蝶状(PY) 2的Ag 6总线) 2一个PY构成订书钉基序2的Ag 2总线) 2根二聚体和四个银离子。此外,发现吡啶配体对硫醇银簇的结构及其Ag-SR键长具有重要影响。
更新日期:2020-09-22
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