Ito Shun, Hirano Koto, Koyasu Kiichirou, Wan Xian-Kai, Wang Quan-Ming, Tsukuda Tatsuya
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, P. R. China.
J Phys Chem Lett. 2024 Nov 7;15(44):11060-11066. doi: 10.1021/acs.jpclett.4c02798. Epub 2024 Oct 29.
Previous studies have reported that [PdAu(PA)] (PA = 3,5-(CF)CHC≡C) with an icosahedral superatomic PdAu(8e) core underwent collision-induced sequential reductive elimination (CISRE) of 1,3-diyne (PA) ( 2020, 124, 19119). The most likely scenario after the CISRE of (PA) is the growth of the PdAu(8e) core via the fusion of the Au(0) atoms produced from the Au(PA) units on the core surface. Contrary to expectation, anion photoelectron spectroscopy and theoretical calculations regarding the CISRE products [PdAu(PA)] ( = 1-6) revealed that the electronically closed PdAu(8e) core does not grow to a single superatom with (8 + 2)e but assembles with Au(2e) units. Characterization of the CISRE products of other alkynyl-protected Au clusters suggested that even the non-superatomic Au(8e) core was resistant to growth due probably to rigidification by PA ligands. We propose that there is a kinetic bottleneck in the growth process of protected Au clusters at the stage where they are electronically closed and/or lose their structural fluxionality by ligation.
