Isomer-Selective Conversion of Au Clusters by Au(I) Thiolate Insertion.

Isomer-selective conversion is a challenging goal in the rational design of Au clusters. Herein, we demonstrate the isomer-selective conversion of Au 18 (S c C 6 ) 14 (S c C 6 = cyclohexanethiolate) into Au 24 (SR) x (S c C 6 ) 20- x in high yields by reactions with gold(I) thiolate (AuSR) complexes. Electrospray ionization mass spectrometry indicated that even numbers of AuSR units are inserted into Au 18 (SR) x (S c C 6 ) 14- x to generate Au 24 (SR) x (S c C 6 ) 20- x through intermediates Au 20 (SR) x (S c C 6 ) 16- x or Au 22 (SR) x (S c C 6 ) 18- x . These results suggest that the number of constituent atoms in surface Au(I)SR oligomers only increases, while the number of electrons in an Au core is maintained. UV-vis analysis revealed the generation of one of two Au 24 (SR) x (S c C 6 ) 20- x isomers in the reactions of Au 18 (S c C 6 ) 14 with AuSR complexes, in contrast to the formation of both isomers by reactions with thiols. When the structures of Au 18 (SR) 14 are compared with those of the Au 24 (SR) 20 isomers, the partial structure in the Au cores is preserved in the isomer-selective conversion with AuSR complexes, regardless of the structures of the thiolate moiety.