Synthesis, X-ray crystal structure and spectroscopic characterization of the new dithiolene [Pd(Et2timdt)2] and of its adduct with molecular diiodine [Pd(Et2timdt)2]·I2·CHCl3 (Et2timdt = monoanion of 1,3-diethylimidazolidine-2,4,5-trithione)

摘要: The first Pd dithiolene [Pd(Et2timdt)2] 4a belonging to the new class of metal dithiolenes deriving from R12timdt (R12timdt = monoanion 1,3-dialkylimidazolidine-2,4,5-trithione) ligand has been characterised by X-ray crystal structure determination on a single [monoclinic, space group P21/n, a = 9.545(2), b = 5.417(2), c = 20.093(4) A, β = 93.40(2)°, Z = 2], UV–VIS–NIR, diffuse solid state reflectance, FTIR, FT-Raman spectroscopies, 13C NMR and cyclic voltammetry results have comparatively discussed with those obtained for analogous [Ni(Et2timdt)2] 4b. UV–VIS–NIR spectrum is dominated very intense absorption band at 1010 nm (e = 70 000 dm3 mol–1 cm–1). NIR features 4b examined basis electronic their ground-state configurations, investigated DFT calculations. co-crystallisation I2 yielded [Pd(Et2timdt)2]·I2·CHCl3 6 adduct C2/m, a = 21.724(9), b = 12.901(4), c = 11.004(6) β = 102.83(4)°, Z = 4]. No short metal–metal interaction was observed in both (Pd· · ·Pd 5.42 A 5.25 6), since each palladium ion almost ‘sandwiched’ between two imidazolidine rings parallel adjacent molecules.