近日，暨南大学李丹团队实现了在1 atm CO压力下，羰基金属化钯纳米簇用于可见光驱动的羰基化反应。2025年7月24日出版的《美国化学会志》发表了这项成果。

钯纳米管在有机合成中具有广阔的应用前景。然而，由于纳米颗粒的形成在动力学上有利，通过直接还原来控制它们的合成仍然具有挑战性。

研究组采用羰基金属酸盐配体调控还原反应动力学，成功地实现了三[Co(Co)₄]终止Pd14 NC。磁性研究，结合量子化学计算，表明Pd14原子团具有四重基态和具有1S1凝胶构型的开壳超原子特征，代表了第一个包含一个自由电子的开壳钯超原子。该材料的高稳定性主要归功于[Co(Co)₄]在Pd(δ^-) - Co（δ⁺）键的极化作用下，随着明显的Co→Pd σ-、π-和δ-供体以及δ-受体，[Co(Co)₄]配体和Pd14核。

值得注意的是，由于[CO(CO)₄]部分增强了亲核活化，Pd14 NC在温和条件下（1 atm CO和30 W的450 nm LED）表现出特殊的羰基化交叉偶联催化活性。该方案可耐受广泛的芳基和烷基卤化物，适用于复杂衍生化和生物活性药物的靶向合成。他们的发现证明了羰基金属酸盐配体在钯热合成中的潜力，并为进一步探索具有独特极性异质金属成分的金属NCs用于协同催化应用提供了可能。

附：英文原文

Title: Carbonylmetallated Palladium Nanoclusters for Visible-Light-Driven Carbonylation under 1 atm of CO

Author: Lin-Mei Zhang, Hui-Zhi Wei, Hao Zhang, Xu-Hang Zhong, Shang-Fu Yuan, Bingzhe Wang, Jianyu Wei, Qixia Bai, Zhe Zhang, Kuan-Guan Liu, Tao Wu, Dan Li

Issue&Volume: July 24, 2025

Abstract: Palladium nanoclusters (Pd NCs) hold great promise in organic synthesis; however their controlled synthesis via direct reduction remains challenging due to kinetically favored formation of nanoparticles. In this study, we employ carbonylmetallate ligands to regulate the reduction reaction kinetics and successfully achieve three [Co(CO)4] terminated Pd14 NCs. Magnetic studies, in conjunction with quantum chemical calculations, suggest that the Pd14 cluster exhibits a quartet ground state and open-shell superatomic character with 1S1 jellium configuration, representing the first open-shell palladium superatom containing one free electron. The high stability of the clusters is largely attributed to significant electron transfer from the [Co(CO)4] ligand to the Pd14 core, facilitated by polarized Pd(δ–)–Co(δ+) bonds, along with pronounced Co→Pd σ-, π-, and δ-donor, as well as δ-acceptor, interactions between the [Co(CO)4] ligands and the Pd14 core. Remarkably, the Pd14 NC exhibits exceptional catalytic activity in carbonylative cross-couplings under mild conditions (1 atm CO and 30 W of 450 nm LEDs), owing to enhanced nucleophile activation by the [Co(CO)4] moieties. This protocol tolerates a broad range of challenging aryl and alkyl halides and is applicable to complex derivatization and the targeted synthesis of bioactive pharmaceuticals. Our findings demonstrate the potential of carbonylmetallate ligands in Pd cluster synthesis and enable further exploration of metal NCs with unique polar heterometallic components for synergistic catalytic applications.

DOI: 10.1021/jacs.5c08034

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c08034