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- Title
Macrocyclic Sulfur Ligand Stabilized Trans‐Palladium Dichloride Complex: Syntheses, Structure, Chlorine Rotation, and Application in α‐Olefination of Nitriles by Primary Alcohols.
- Authors
Kumar, Sunil; Sharma, Ashutosh; Mahala, Suman; Gaatha, K.; Reddy, S. Rajagopala; Rom, Tanmay; Paul, Avijit Kumar; Roy, Partha; Joshi, Hemant
- Abstract
Herein, we have reported the synthesis of a macrocyclic organosulfur ligand (L1) having a seventeen‐membered macrocyclic ring. Subsequently, the corresponding trans‐palladium complex (C1) of bulky macrocyclic organosulfur ligand (L1) was synthesized by reacting it with PdCl2(CH3CN)2 salt. The newly synthesized ligand and complex were characterized using various analytical and spectroscopic techniques. The complex showed a square planar geometry with trans orientation of two ligands around the palladium center. The complex possesses intramolecular SCH...Cl interactions of 2.648 Å between the macrocyclic ligand and palladium dichloride. The potential energy surface (PES) for the rotational process of C1 suggested a barrier of ~23.81 kcal/mol for chlorine rotation. Furthermore, the bulky macrocyclic organosulfur ligand stabilized palladium complex (C1) was used as a catalyst (2.5 mol %) for α‐olefination of nitriles by primary alcohols. The α,β‐unsaturated nitrile compounds were found to be the major product of the reaction (57–78 % yield) with broad substrate scope and large functional group tolerance. Notably, the saturated nitrile product was not observed during the reaction. The mechanistic studies suggested the formation of H2 and H2O as only by‐products of the reaction, thereby making the protocol greener and sustainable.
- Subjects
SCHIFF bases; POTENTIAL energy surfaces; CHLORINE; NITRILES; SULFUR; ROTATIONAL motion
- Publication
Chemistry - An Asian Journal, 2024, Vol 19, Issue 4, p1
- ISSN
1861-4728
- Publication type
Article
- DOI
10.1002/asia.202300935