Synthesis and characterization of two vic-dioximes containing the 1,3-dioxolane ring and 1,4-diaminobutane and their cobalt(II), nickel(II), copper(II) and zinc(II) metal complexes Erdal Canpolat and Mehmet Kaya* Department of Chemistry, Faculty of Art and Sciences, University of Firat, 23119 Elazi  g, Turkey Received 16 December 2003; accepted 29 January 2004 Abstract Two new vic-dioxime ligands, (E,E)-N-{4-[(1,4-dioxaspiro[4.4]non-2-ylmethyl)amino]butyl}-N¢-hydroxy-2-(hydrox- yimino)ethanimidamide (L 1 H 2 ) and (E,E)-N-{4-[(1,4-dioxaspiro[4.5]dec-2-ylmethyl)amino]butyl}-N¢-hydroxy-2- (hydroxyimino)ethanimidamide (L 2 H 2 ) containing two different heteroatoms (N,O) have been prepared from anti-chloroglyoxime, N-(1,4-dioxaspiro[4.4]non-2-ylmethyl)butane-1,4-diamine (3) and N-(1,4-dioxaspiro[4.5]dec-2- ylmethyl)butane-1,4-diamine (4). Co II , Ni II and Cu II complexes of the ligands have a metal:ligand ratio of 1:2 and the ligands coordinate through the two N atoms, as do most of the vic-dioximes. However, Zn II complexes of the ligands have a metal:ligand ratio of 1:1 and the ligands are coordinated only by the N, O atoms of the vic-dioximes. In the Co II complexes two water molecules, and in the Zn II complexes a chloride ion and a water molecule, are also coordinated to the metal ion. The structures of the compounds were determined by a combination of elemental analysis, magnetic moments, molar conductances, thermogravimetric analysis (t.g.a.) and spectroscopic (u.v.–vis., i.r., 1 H- and 13 C-n.m.r.) data. Introduction The high stability of complexes prepared from vic- dioxime ligands has been extensively used for various purposes such as trace metal analyses [1, 2]. Because of its importance, the chemistry of transition metal com- plexes with vic-dioxime ligands has been extensively investigated [3]. Some oximes are widely used for various purposes in organic, inorganic, bioinorganic, pigment, analytical, dyes and medical chemistry [4, 5]. Vic-dioximes, containing mildly acidic hydroxyl groups and slightly basic nitrogen atoms, are amphoteric and their transition metal complexes have been investigated widely as analytical reagents and as models for biolog- ical systems such as vitamin B 12 [6]. The geometrical isomers of vic-dioximes and their derivatives depending on the position of the hydroxyl groups in the molecule are syn-, anti- and amphi- structures. Usually, the stability order of these is the anti>amphi>syn config- uration, but there are some exceptions [7]. Among the three isomers, namely anti-, amphi- and syn- the first is more liable and forms N,N-coordinated planar complexes stabilized by hydrogen bonding [8]. Compounds containing the 1,3-dioxolone groups are used as solvents, additives and as corrosion retardants. Polymers containing the 1,3-dioxolane groups exhibit semiconducting behavior, while some polymers and copolymers of 1,3-dioxolane exhibit herbicidal and perfume activity [9, 10]. The results of our investigations on the synthesis, characterization and spectroscopic studies of cobalt(II), nickel(II), copper(II) and zinc(II) complexes with the title ligands (L 1 H 2 and L 2 H 2 ) shown in (Figure 1) are reported in the present paper. Experimental Materials The preparation of anti-chloroglyoxime has been described previously [11]. All the reagents used were purchased from Merck, Fluka or the Sigma Company and are chemically pure. Physical measurements Elemental analyses (C, H, N) were performed on a LECO-932 CHNSO elemental analysis apparatus (Table 1). I.r. spectra were recorded on a Mattson 1000 FT-IR spectrometer as KBr pellets and using a NaCl cell. 1 H- and 13 C-n.m.r. spectra were recorded on a JEOL FX-90Q FT-NMR and Bruker GmbH Dpx-400 MHz High Performance Digital FT-NMR Spectrome- ters in DMSO-d 6 . Electronic spectra were obtained on a Shimadzu 1240 UV Spectrophotometer. Magnetic sus- * Author for correspondence Transition Metal Chemistry 29: 550–556, 2004. 550 Ó 2004 Kluwer Academic Publishers. Printed in the Netherlands.