Free Metallophosphines: Extremely Electron-Rich Phosphorus Superbases That Are Electronically and Sterically Tunable**

Wei，Rui; Ju，Shaoying; Liu，Liu Leo

2022-07-11

10.1002/anie.202205618

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Impact Factor & Quartile

1433-7851

1521-3773

We report herein a facile and highly modular access to an intriguing class of free Au-substituted phosphines (AuPhos), namely (LAu)PR (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.

Ligand Design Metal Substituents Phosphines Superbases Transition Metal Catalysis

SCI ; EI

English

NI Journal Papers

First ; Corresponding

Natural Science Foundation of Guangdong Province[2022A1515011717];National Natural Science Foundation of China[22101114];

WOS:000795000000001

20222012125297

Catalysis ; Electrons ; Iridium compounds ; Ligands ; Metal complexes ; Phosphorus compounds ; Transition metals

Metallurgy and Metallography:531 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2

CHEMISTRY

2-s2.0-85132619864

Scopus

Department of Chemistry,Shenzhen Grubbs Institute and Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,518055,China

Wei，Rui,Ju，Shaoying,Liu，Liu Leo. Free Metallophosphines: Extremely Electron-Rich Phosphorus Superbases That Are Electronically and Sterically Tunable**[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2022,61(28).

Wei，Rui,Ju，Shaoying,&Liu，Liu Leo.(2022).Free Metallophosphines: Extremely Electron-Rich Phosphorus Superbases That Are Electronically and Sterically Tunable**.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,61(28).

Wei，Rui,et al."Free Metallophosphines: Extremely Electron-Rich Phosphorus Superbases That Are Electronically and Sterically Tunable**".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61.28(2022).