A Face-to-Face Dimer of Au Superatoms Supported by Interlocked Tridentate Scaffolds Formed in Au S (SR).

A new sulfur-containing gold cluster, Au S (STipb) , was serendipitously obtained using the bulky thiol, 2,4,6-triisopropylbenzyl mercaptan (TipbSH), as protecting ligands. Single-crystal X-ray diffraction analysis revealed that Au S (STipb) has a deformed octahedral Au core clutched by two tridentate S[Au (STipb) ] units in an interlocked manner. Based on density functional theory calculations, we propose that the Au core with two electrons is better viewed as a face-to-face dimer of Au (1e) superatoms rather than an electronically closed Au (2e) superatom. In situ formation of the sulfide anions (S ) via C-S bond breakage is ascribed to the steric repulsion between the TipbS ligands.