Five complexes containing N,N-bis(2-hydroxyethyl)-ethylenediamine with tetracyanidopalladate(II): synthesis, crystal structures, thermal, magnetic, and catalytic properties

Abstract

Five cyanide complexes, [Ni(N-bishydeten)Pd(CN)4] (1), [Cu(N-bishydeten)Pd(μ-CN)2(CN)2]n (2), [Cu(N-bishydeten)2][Pd(CN)4] (3), [Zn(N-bishydeten)Pd(CN)4] (4), and [Cd(N-bishydeten)2][Pd(CN)4] (5) (N-bishydeten = N,N-bis(2-hydroxyethyl)-ethylenediamine), have been synthesized and characterized using various techniques. Different structures were formed when the M : L ratio was varied in copper complexes. The single-crystal X-ray diffraction analysis reveals that 2, a 1-D cyanide-bridged complex with 2,2-CT-type zigzag chain, was obtained by using 1 : 1 M : L ratio whereas 3 was formed as a complex salt in a molar ratio of 1 : 2. The thermal stabilities determined from DTGmax values of the first decomposition stages change in the order 1 > 5 > 4 > 3 > 2. Although an EPR signal was not observed for 1, the g parameters obtained from the EPR spectra of 2 and 3 indicate that CuII ions are located in tetragonally distorted octahedral sites (D 4h), and the ground state of the unpaired electron is (2B1g). The magnetic behavior indicates a very small antiferromagnetic interaction below 10 K for 1–3. In 3, there is a temperature-independent paramagnetism (α) due to the orbital moments of the d electrons. 1–3 were tested as catalysts in Suzuki and Heck coupling reactions.