南方科技大学刘柳团队合成了电子和空间可调的富电子磷超基，自由金属膦。相关研究成果发表在2022年5月3日出版的国际学术期刊《德国应用化学》。

该文中，研究人员报告了一种简便且高度模块化的方法，可以获得一类有趣的自由金取代膦（AuPhos），即（LAu）nPR3-n（L=单线态卡宾配体；R=H，芳基，烷基，硅基）（n=1-3）。托尔曼电子参数（TEP）值与理论相结合研究表明，Au取代可以提高AuPhos的电子释放能力，从而形成电子和空间可调、极富电子的磷中心。

AuPhos的高碱度归因于Au取代基与p处的孤对相互作用产生的d-p孤对π-排斥作用。AuPhos连接的一系列多核过渡金属配合物（即Rh、Ir、Pd、Au、W、Mn）可通过简单的工艺制备。初步催化结果表明，钯催化的C-N偶联反应和红外催化的脱羰反应都是通过AuPhos进行的。

该项工作为富电子配体的未来发展提供了见解。

附：英文原文

Title: Free Metallophosphines: Extremely Electron-Rich Phosphorus Superbases that are Electronically and Sterically Tunable

Author: Rui Wei, Shaoying Ju, Liu Leo Liu

Issue&Volume: 2022-05-03

Abstract: We report herein a facile and highly modular access to an intriguing class of free Au-substituted phosphines (AuPhos), namely (LAu)nPR3-n (L = singlet carbene ligand; R = H, aryl, alkyl, silyl) (n = 1-3). The Tolman electronic parameter (TEP) values coupled with theoretical investigations showcase that Au-substitution can boost the electron-releasing ability of AuPhos, thus leading to an electronically and sterically tunable, extremely electron-rich phosphorus center. The high basicity of AuPhos is attributed to the d-p lone pair π-repulsion arising from interaction between Au substituents and the lone pair at P. A series of multi-nuclear transition metal complexes (i.e. Rh, Ir, Pd, Au, W, Mn) ligated by AuPhos are readily prepared via a straightforward process. Preliminary catalytic results reveal the facilitation of Pd-catalyzed C-N coupling reactions and Ir-catalyzed decarbonylation reactions via AuPhos. This work provides insights for future development of electron-rich ligands.

DOI: 10.1002/anie.202205618

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202205618