Ag(I) Complexes of Imine Derivatives of Unexpected 2-Thiophenemethylamine Homo-Coupling and Bis-(E)-N-(furan-2-ylmethyl)-1-(quinolin-2-yl)methanimine

Abstract

Imines are fundamental organic compounds used as synthetic intermediates and as ligands in coordination chemistry. They are also found to be important pharmacophores in various bioactive compounds. In this report, two Schiff bases were prepared using the traditional condensation of 4-pyridinecarboxaldehyde with 2-thiophenemethylamine and 2-quinolinecarboxaldehyde with furfurylamine to form (E)-1-(pyridin-4-yl)-N-(thiophen-2-ylmethyl)methanimine (L1) and (E)-N-(furan-2-ylmethyl)-1-(quinolin-2-yl)methanimine (L2) respectively. L1 and L2 were complexed with silver perchlorate in 2:1 [M:L] stoichiometry to obtain complexes 1 and 2, respectively. The crystal structures of 1 and 2 were unequivocally determined by single-crystal X-ray diffraction analysis. The resulting structures revealed 2 to be a four-coordinate as expected. In contrast, an unexpected chemoselective hydrolytic cleavage of one mole of the (CH=N) imine ligands occurred in complex 2 and, further, the amines (thiophenemethylamine) homo-coupled to form a new imine ligand derivative in situ (L1a) before coordinating to the Ag(I) center along with L1. This observation described an alternative synthetic route to be explored to synthesize a diverse range of imine derivatives, which involves the Ag(I)-promoted homo-coupling of amines. Herein, the crystal structures of Ag(I) complexes of pyridinyl [Ag(L1)(L1a)]ClO4 (1) and quinolinyl [Ag(L2)2]ClO4 (2) Schiff bases are presented.