Ion-Pairing Chirality Transfer in Atropisomeric Biaryl-Centered Gold Clusters  

作　　者：Kui Xiao Yang Xue Biao Yang Liang Zhao 

机构地区：[1]Key Laboratory of Bioorganic Phosphorus Chemistry&Chemical Biology(Ministry of Education),Department of Chemistry,Tsinghua University,Beijing 100084

出　　处：《CCS Chemistry》2021年第1期555-565,共11页中国化学会会刊（英文）

基　　金：National Natural Science Foundation of China(21772111,21821001,91956125,and 21661132006).

摘　　要：The stereocontrol of chiral metal clusters and nanoclusters has become a focus of interest in metal cluster chemistry due to their promising applications in asymmetric catalysis.Despite being a general chirality transfer strategy,the ion-pairing process is still ambiguous in the course of bestowing chirality to metal clusters.Here we construct a biaryl-centered axially chiral gold-cluster system to study an outside-in ion-pairing chirality transfer process.Four hexanuclear gold(I)clusters,centered by two types of biaryl ligands[(2-indolyl)aniline(L^(1))and biindole(L^(2))],were synthesized via in situ cyclization reactions.In the crystalline state,the biaryl centers showed axial chirality in which the gold atoms were in an asymmetric arrangement.In solution,the chiral phosphates induced an outside-in chirality transfer by significant interactions with the periphery of the biaryl-centered gold clusters.Finally,the chiral resolution of hexa-aurated biindoliums was accomplished via an efficient outside-in chirality transfer process relying on strong aurophilic interaction and extra peripheral coordination.This study not only deepens the understanding of the outside-in ion-pairing chirality transfer process but also provides a new approach for fabricating desired chiral metal clusters by a combination of organometallic transformation and chirality transfer.

关 键 词：axial chirality biaryl ligand chirality transfer gold cluster ION-PAIRING 

分 类 号：O62[理学—有机化学]