Ketimine synthesis in the coordination sphere of thallium (I)

[AuTl(C6F5)2(en)] (en = ethylenediamine) reacts with cyclic ketones as cyclopentanone (Cy5O), cyclohexanone (Cy6O) or cycloheptanone (Cy7O) in 1:1 or 1:2 molar ratio leading to products of stoichiometry [AuTl(C6F5)2{CyxN(CH2)2NH2}] (x = 5 1, 6 2 or 7 3), or [AuTl(C6F5)2{CyxN(CH2)2NCyx}] (x = 5 4, 6 5 or 7 6). Addition of ethylenediamine to the ketimine complexes in chloroform regenerates [AuTl(C6F5)2(en)], the starting material, and the free ketimines, as their NMR and mass spectra evidenced. The ketimine complexes display luminescence in solid state at room temperature and at 77 K at higher wavelengths than the diamine starting product (505 nm). The excited states responsible for this behaviour are assigned to orbitals due to the gold–thallium interactions.