Five complexes containing N,N-bis(2-hydroxyethyl)- ethylenediamine with tetracyanidopalladate(II): synthesis, crystal structures, thermal, magnetic, and catalytic properties Ş. ASLAN KORKMAZ†, A. KARADAĞ*‡, N. KORKMAZ‡, Ö. ANDAÇx N. GÜRBÜZ{, İ. ÖZDEMIR{ and R. TOPKAYAk †Aquaculture Department, Vocational College, Tunceli University, Tunceli, Turkey zChemistry Department, Gaziosmanpaşa University, Tokat, Turkey xChemistry Department, Ondokuz Mayıs University, Samsun, Turkey {Chemistry Department, İnönü University, Malatya, Turkey kPhysics Department, Gebze Institute of Technology, Kocaeli, Turkey (Received 4 March 2013; in final form 6 June 2013) 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 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 d x 2 Ày 2 ( 2 B 1g ). 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. Keywords: Tetracyanidopalladate; N,N-bis(2-hydroxyethyl)-ethylenediamine; Thermal analysis; Magnetic susceptibility; Suzuki–Heck coupling reaction 1. Introduction The wide availability of transition metal cyanide complexes in terms of both diverse bonding and structural chemistry has led to widespread application of these complexes in materials chemistry. Cyanide is an efficient ligand for stabilization and the formation of one- (1-D), two- (2-D), or three-dimensional (3-D) structures. The versatility of cyanide results from its ability to act as both a σ-donor and a π-acceptor, its negative charge, and its ambidentate nature [1]. A terminal cyanide can participate in simple hydrogen bonds of *Corresponding author. Email: ahmet.karadag@gop.edu.tr Journal of Coordination Chemistry , 2013 Vol. 66, No. 17, 3072–3091, http://dx.doi.org/10.1080/00958972.2013.820827 Ó 2013 Taylor & Francis