Five Complexes Containing N, N -Bis(2 With Tetracyanidopalladate(II): Synthesis, Crystal Structures, Thermal, Magnetic, and Catalytic Properties

Abstract

Five cyanide complexes, [Ni(N-bishydeten)Pd(CN)<inf>4</inf>] (1), [Cu(N-bishydeten)Pd(-CN)<inf>2</inf>(CN)<inf>2</inf>]<inf>n</inf> (2), [Cu(N-bishydeten)<inf>2</inf>][Pd(CN)<inf>4</inf>] (3), [Zn(N-bishydeten)Pd(CN) <inf>4</inf>] (4), and [Cd(N-bishydeten)<inf>2</inf>][Pd(CN)<inf>4</inf>] (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 (D4<inf>h</inf>), and the ground state of the unpaired electron is ( 2B1<inf>g</inf>). 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. © 102013 © 2013 Taylor & Francis.