Resistance of a PdAu₁₂(8e) Core to Growth in Collision-Induced Sequential Reductive Elimination of (C≡CR)₂ from [PdAu₂₄(C≡CR)₁₈]².

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters Pub Date : 2024-11-07 Epub Date: 2024-10-29 DOI:10.1021/acs.jpclett.4c02798

Shun Ito, Koto Hirano, Kiichirou Koyasu, Xian-Kai Wan, Quan-Ming Wang, Tatsuya Tsukuda

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Abstract

Previous studies have reported that [PdAu₂₄(PA^F)₁₈]^2- (PA^F = 3,5-(CF₃)₂C₆H₃C≡C) with an icosahedral superatomic PdAu₁₂(8e) core underwent collision-induced sequential reductive elimination (CISRE) of 1,3-diyne (PA^F)₂ ( J. Phys. Chem. C 2020, 124, 19119). The most likely scenario after the CISRE of (PA^F)₂ is the growth of the PdAu₁₂(8e) core via the fusion of the Au(0) atoms produced from the Au₂(PA^F)₃ units on the core surface. Contrary to expectation, anion photoelectron spectroscopy and theoretical calculations regarding the CISRE products [PdAu₂₄(PA^F)_18-2n]^2- (n = 1-6) revealed that the electronically closed PdAu₁₂(8e) core does not grow to a single superatom with (8 + 2n)e but assembles with Au₂(2e) units. Characterization of the CISRE products of other alkynyl-protected Au clusters suggested that even the non-superatomic Au₁₇(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.

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PdAu12(8e) 内核在[PdAu24(C≡CR)18]2 碰撞诱导 (C≡CR)2 顺序还原消解过程中的生长阻力。

先前的研究报告称，具有二十面体超原子 PdAu12(8e) 内核的 [PdAu24(PAF)18]2- (PAF = 3,5-(CF3)2C6H3C≡C) 经历了 1,3 二炔 (PAF)2 的碰撞诱导顺序还原消除 (CISRE) ( J. Phys. Chem. C 2020, 124, 19119)。(PAF)2发生CISRE后最可能的情况是，通过核表面Au2(PAF)3单元产生的Au(0)原子的融合，PdAu12(8e)核增长。与预期相反，阴离子光电子能谱和有关 CISRE 产物 [PdAu24(PAF)18-2n]2- （n = 1-6）的理论计算显示，电子封闭的 PdAu12(8e) 内核并没有成长为具有 (8 + 2n)e 的单个超原子，而是与 Au2(2e) 单元组装在一起。对其他炔基保护金簇的 CISRE 产物进行的表征表明，即使是非超原子的 Au17(8e) 内核也可能由于 PA 配体的刚性化而无法生长。我们认为，在受保护金簇的生长过程中，在其电子封闭和/或因连接而失去结构通性的阶段存在一个动力学瓶颈。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

The Journal of Physical Chemistry Letters CHEMISTRY, PHYSICAL-NANOSCIENCE & NANOTECHNOLOGY

CiteScore

9.60

自引率

7.00%

发文量

1519

审稿时长

1.6 months

期刊介绍： The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.