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Mechanism of Nucleation of Gold(I) Thiolate Oligomers into Gold–Thiolate Nanoclusters
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posted on 2022-03-29, 20:03 authored by Lanyan Li, Pu Wang, Yong PeiThe mechanism of reductive synthesis
of gold–thiolate nanoclusters
from gold(I)–thiolate oligomers under boron hydride (BH4–) reduction is studied based on ab initio
molecular dynamics (AIMD) simulations and density functional theory
(DFT) calculations. The AIMD simulations show that the interaction
between BH4– and the gold(I)–thiolate
oligomers leads to formation of active intermediates containing an
Au–H or an Au–H–Au moiety, instead of direct
formation of HSR and Au–Au bonds. The active intermediates
interact with the gold(I)–thiolate oligomers or other active
intermediates to form Au–Au bonds and 2e– building blocks. In the present studies, the pathways of formation
of 2e– building blocks from the active intermediate
species are proposed and verified by the DFT calculations, which indicate
that the hydride on Au–H and Au–H–Au moieties
acts as a nucleophilic agent to attack gold atoms and lead to formation
of new Au–Au bonds. The newly discovered nucleation mechanism
is applied to understand the formation of 2e– cluster
Au15(SR)13 and 4e– cluster
Au16(SR)12.
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Keywords
sup >– supdensity functional theoryactive intermediate speciesau – hactive intermediates interactactive intermediates containingattack gold atoms13 sub)– thiolate oligomersaimd simulations showactive intermediatesthiolate oligomerscluster austudied basedreductive synthesispresent studiesnucleophilic agentgold (building blocks