Published: Aug. 6, 2024
Pd(0) oxidative addition (OA) to organic halides is a fundamental step in many catalytic transformations. Previous mechanistic studies have shown that the electronic/steric nature of ligand, metal coordination unsaturation, halide identity and presence an additive all sizable influences on reaction reactivity selectivity. A single parameter-based rational design fully integrating important factors quantitative manner remains elusive, due complex OA. To address this challenge, study Pd(0)-halide interactions which are crucial for 3-centered concerted mechanism, initiated work by key progress organometallic chemistry relatively well-established halogen bonding knowledge, mimicking “data-driven” method. The achieved advanced understanding mechanisms includes five parts: 1) uncovering “super iodine” character Pd(0), 2) Pd-halide (organic halide) interaction its essential role Pd(organic precomplex before OA; 3) molecular mechanism effect, theoretical prediction transfer pathway OA specific halides; 4) demystifying known super ligand-controlled Pd catalysis with inactive aryl chlorides; ultimately 5) proposing proof-of-concept surface molecule electrostatic potential-based
Language: Английский