Abstract
Synthesis of mixed monolayer-protected Au clusters (MPCs) from unsymmetrical disulfides (HO(CH2)11SS(CH2)11CH3) yields clusters with a 1:1 composition of HO(CH2)11S− and CH3(CH2)11S− thiolates, whereas products from reaction of a 1:1 mixture of thiols (HO(CH2)11SH and CH3(CH2)11SH) contain mostly (97%) HO(CH2)11S− ligands in the monolayer. The results suggest a thermodynamically preferred ligation of HO(CH2)11SH over CH3(CH2)11SH that is circumvented in the disulfide reaction. The core sizes of MPCs synthesized from alkanethiol and dialkyl disulfides are similar, suggesting similar MPC growth dynamics for thiols and disulfides. The compositions of MPCs synthesized starting from gold(I)−thiolate polymer intermediates suggest that the polymer undergoes immediate breakup upon addition of reductant.
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