期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 2, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202113275
关键词
bulky thiolates; gold superatoms; interlocked cage structures; sulfide ligands
资金
- JST CREST [JPMJCR20B2]
- Elements Strategy Initiative for Catalysts & Batteries (ESICB) from MEXT [JPMXP0112101003]
- Advanced Characterization Nanotechnology Platform from MEXT [JPMXP09A20UT0024]
- KAKENHI grant from JSPS [20H00370]
The structure of the new sulfur-containing gold cluster Au18S2(STipb)(12) was revealed through single-crystal X-ray diffraction analysis, showing a deformed octahedral Au-6 core clutched by two tridentate S[Au-2(STipb)(2)](3) units in an interlocked manner.
A new sulfur-containing gold cluster, Au18S2(STipb)(12), was serendipitously obtained using the bulky thiol, 2,4,6-triisopropylbenzyl mercaptan (TipbSH), as protecting ligands. Single-crystal X-ray diffraction analysis revealed that Au18S2(STipb)(12) has a deformed octahedral Au-6 core clutched by two tridentate S[Au-2(STipb)(2)](3) units in an interlocked manner. Based on density functional theory calculations, we propose that the Au-6 core with two electrons is better viewed as a face-to-face dimer of Au-3(1e) superatoms rather than an electronically closed Au-6(2e) superatom. In situ formation of the sulfide anions (S-2- via C-S bond breakage is ascribed to the steric repulsion between the TipbS ligands.y
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