Chiroptical activity of BINAP-stabilized undecagold clusters.
Chiroptical activity of BINAP-stabilized undecagold clusters.
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DOI：
10.1021/jp061670f
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发表时间：
2006-05
期刊：
影响因子：
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通讯作者：
Yasushi Yanagimoto;Y. Negishi;H. Fujihara;T. Tsukuda
中科院分区：
文献类型：
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作者：
Yasushi Yanagimoto;Y. Negishi;H. Fujihara;T. Tsukuda
通过化学还原相应的前体化合物Au2X2(BINAP)，合成了十一碳簇合物[AU11(BINAP)4X2]+(X=Cl和Br.)，其中BINAP代表双齿膦配体2，2‘-二(二苯基膦)-1，1’-联萘.由对映体[Au11(R-BINAP)4X2]+和[Au11(S-BINAP)4X2]+稳定的Au11(3+)的圆二色谱表现出强烈的镜象Cotton效应，而由非手性单齿膦配体稳定的Au11(3+)簇的圆二色谱则没有。在AU11(3+)核结构形变的背景下，讨论了[AU11(BINAP)4X2]+手性活性的来源。
Undecagold cluster compounds [Au11(BINAP)4X2]+ (X = Cl and Br) were synthesized by chemical reduction of the corresponding precursor complexes, Au2X2(BINAP), where BINAP represents the bidentate phosphine ligand 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl. The circular dichroism spectra of Au11 stabilized by the enantiomers [Au11(R-BINAP)4X2]+ and [Au11(S-BINAP)4X2]+ exhibited intense and mirror-image Cotton effect, whereas those of Au11(3+) clusters stabilized by achiral monodentate phosphine ligands did not. The origin of the chiroptical activity of [Au11(BINAP)4X2]+ is discussed in the context of the structural deformation of the Au11(3+) core.