N-bonding vs. S-bonding in thiocyanato-copper(II) complexes
2011
Mautner, Franz A. | Albering, Jörg H. | Harrelson, Emily V. | Gallo, August A. | Massoud, Salah S.
Three mononuclear thiocyanato-Cu(II) complexes have been synthesized: the mono-thiocyanato [Cu(cyclen-tpam)(NCS)]ClO₄·3H₂O (1) and [Cu(DPA)(NCS)ClO₄] (2), and the dithiocyanato complex Cu(bdmpzpy)(NCS)₂ (3), where cyclen-tpam=1,4,7,10-tetrakis(propionamide)-1,4,7,10-tetraazacyclododecane, DPA=bis(2-pyridylmethyl)amine, and bdmpzpy=2,6-bis[(2,5-dimethyl-1-pyrazolyl)methyl]pyridine. The single crystal X-ray crystallography of the complexes confirmed the perfect square pyramidal geometry (SP) in 1 and distorted SP geometry in 2 and 3 with N-bonding coordination mode for the thiocyanato ligands. The IR spectra of the complexes which were consistent with the N-bonding coordination mode of the thiocyanate group(s) and the visible spectra which revealed the square pyramidal geometry around the central Cu²⁺ ion were in complete agreement with the X-ray structural determination.
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