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(-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 1:1M:L ratio whereas 3 was formed as a complex salt in a molar ratio of 1:2. The thermal stabilities determined from DTG(max) 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 Cu-II ions are located in tetragonally distorted octahedral sites (D-4h), and the ground state of the unpaired electron is (B-2(1g)). The magnetic behavior indicates a very small antiferromagnetic interaction below 10K for 1-3. In 3, there is a temperature-independent paramagnetism () due to the orbital moments of the d electrons. 1-3 were tested as catalysts in Suzuki and Heck coupling reactions.