Calcium‐Ligand Cooperation Promoted Activation of N2O, Amine, and H2 as well as Catalytic Hydrogenation of Imines, Quinoline, and Alkenes.

Bond activation and catalysis using s‐block metals are of great significance. Herein, a series of calcium pincer complexes with deprotonated side arms have been prepared using pyridine‐based PNP and PNN ligands. The complexes were characterized by NMR and X‐ray crystal diffraction. Utilizing the obtained calcium complexes, unprecedented N2O activation by metal‐ligand cooperation (MLC) involving dearomatization‐aromatization of the pyridine ligand was achieved, generating aromatized calcium diazotate complexes as products. Additionally, the dearomatized calcium complexes were able to activate the N−H bond as well as reversibly activate H2, offering an opportunity for the catalytic hydrogenation of various unsaturated molecules. DFT calculations were applied to analyze the electronic structures of the synthesized complexes and explore possible reaction mechanisms. This study is an important complement to the area of MLC and main‐group metal chemistry. [ABSTRACT FROM AUTHOR]