Mono and Dinuclear Palladium Pincer Complexes of NNSe Ligand as a Catalyst for Decarboxylative Direct C−H Heteroarylation of (Hetero)arenes
Sohan Singh, Vikki N. Shinde, Sunil Kumar, Neha Meena, Nattamai Bhuvanesh, Krishnan Rangan, Anil Kumar, Hemant Joshi
Abstract
Abstract This report describes the synthesis of a new NNSe pincer ligand and its mono‐ and dinuclear palladium(II) pincer complexes. In the absence of a base, a dinuclear palladium pincer complex ( C1 ) was isolated, while in the presence of Et 3 N base a mononuclear palladium pincer complex ( C2 ) was obtained. The new ligand and complexes were characterized using techniques like 1 H, 13 C{ 1 H} nuclear magnetic resonance (NMR), fourier transform infrared (FTIR), high‐resolution mass spectrometry (HRMS), ultraviolet‐visible (UV‐Visible), and cyclic voltammetry. Both the complexes showed pincer coordination mode with a distorted square planar geometry. The complex C1 has two pincer ligands attached through a Pd−Pd bond in a dinuclear pincer fashion. The air and moisture‐insensitive, thermally robust palladium pincer complexes were used as the catalyst for decarboxylative direct C−H heteroarylation of (hetero)arenes. Among the complexes, dinuclear pincer complex C1 showed better catalytic activity. A variety of (hetero)arenes were successfully activated (43–87 % yield) using only 2.5 mol % of catalyst loading under mild reaction conditions. The PPh 3 and Hg poisoning experiments suggested a homogeneous nature of catalysis. A plausible reaction pathway was proposed for the dinuclear palladium pincer complex catalyzed decarboxylative C−H bond activation reaction of (hetero)arenes.