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Updated: Aug 5, 2026

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Twisted amide Xantphos ligands: wide bite angle, twist-controlled diphosphines
Wenchao Chu1, Tongliang Zhou1, Guangchen Li1
1Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ 07102, USA. michal.szostak@rutgers.edu.
Abstract:
Xantphos ligands are among the most significant bis(phosphines) developed in the field of homogeneous catalysis. Twisted amides have been established to have a pronounced impact on the geometry of substituents attached to the amide linkage. Herein, we describe the synthesis, structural characterization and activity of novel, easily accessible twisted amide Xantphos ligands. These ligands feature controlled P-P distances and increased P-M-P bite angles guided by the amide bond twist and geometry. Notably, N-t-BuC(O)-Xantphos, which exhibits significant amide nitrogen pyramidalization (χN = 32°), showed enhanced catalytic efficiency toward C-C, C-P, and C-B bond-forming reactions. Steric properties and coordination chemistry with Au(I), Cu(I), and Pd(II) are presented. Considering the critical role of phosphine ligands and twisted amides in chemistry, the concept of controlling bis(phosphines) geometry by amide bond twist is anticipated to gain rapid and widespread adoption.
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