Synthesis and Characterization of a Novel Macrocyclicvic-Dioxime and Some of its Mono and Trinuclear Complexes

Abstract

The (E, E)-dioxime containing a dithia-dioxa-diaza macrocyclic moiety 5,6 : 11,12 : 17,18-tribenzo-2,3-bis(hydroxyimino)-1,4-diaza-7,16-dithia-10,12-dioxacyclooctadecane (H 2 L) has been synthesized in high yield by a 1 + 1 addition of cyanogendi-N-oxide with 2, 3 : 8,9 : 14,15-tribenzo-1,16-diamino-4,13-dithia-7,10-dioxahexadecane (3) which was obtained from condensation reaction with 2-amino thiophenol and 1,2-bis(2-bromoethoxy)benzene, in dichloromethane at ±10°C. Two vic-Dioxime ligands coordinate with Ni(II), Cu(II) and Co(III) through its hydroxyimino nitrogen donor atoms by the loss of the oxime protons. Homo and heterotrinuclear Cu II 3 and Co III Pd II 2 complexes of this ligand have been prepared; their two ligand molecules are connected via hydroxyimino or BF 2 + -bridging groups and two of the metal ions are coordinated by a diaza-dithia mixed donor macrocyclic moiety. The macrocyclic ligand and its transition metal complexes have been characterized on the basis of 1 H-, 13 C-NMR, IR and MS spectroscopy and elemental analysis data. Synthese und Charakterisierung eines neuen vic-Dioxim-Makrocyclus und einiger seiner mono-und trinuklearen MetallkomplexeInhaltsu È bersicht. Das (E,E)-Dioxim mit dem Dithia-dioxodiaza-Makrocyclus 5,6 : 11,12 : 17 : 18-Tribenzo-2,3-bis(hydroxyimino)-1,4-diaza-7,16-dithia-10,12-dioxacyclooctadecan (H 2 L) wurde in hohen Ausbeuten synthetisiert durch 1 + 1 Addition von Dicyan-di-N-oxid mit 2,3 : 8,9 : 14,15-tribenzo-1,16-diamino-4,13-dithia-7,10-dioxahexadecan (3), das durch Kondensationsreaktion von 2-Aminothiophenol und 1,2-Bis(2-bromethoxy)benzol in Dichlormethan bei ±10°C erhalten wurde. Zwei vic-Dioximliganden koordinieren mit Ni II , Cu II bzw. Co III u È ber die Hydroxoimino-Stickstoffatome unter Verlust der Oximprotonen. Homo-und heteronukleare Cu II 3 -und Co III Pd II 2 -Komplexe dieses Liganden wurden dargestellt; ihre beiden Ligandenmoleku È le sind u È ber Hydroxoimino-oder BF 2 + -Bru È cken verbunden und zwei der Metallionen werden durch die N-und S-Donoratome der makrocyclischen Einheit koordiniert. Der makrocyclische Ligand und seine Ûbergangsmetallkomplexe wurden durch 1 H-, 13 C-NMR-, IR-, MS-Spektroskopie sowie durch Elementaranalysen charakterisiert.

A new vic-dioxime ligand containing two azo substituents and its mononuclear nickel(II), cobalt(II), and copper(II) complexes; synthesis, characterization, spectroscopic and biological studies

“…The past decade has included studies on their syntheses and characterization [10,11], preparation of their mono-nuclear [12][13][14], homo- [15] and hetero-polynuclear [16,17], and polymeric metal complexes [18][19][20]. Flourescence [21], optical [22][23][24], biological [25,26], electrochemical [27][28][29], and thermal properties [30,31] have been of particular interest.…”

Alcohol-soluble functional vic-dioxime bearing alcoholhexylsulfanyl moieties: preparation, spectroscopy and electrochemistry

“…The polar moieties increase the hydrophilicity of (1), and enhance its solubility in organic polar solvents. (2), Cu II (3), Co II (4) Mn II (5) and Pd II (6)] (Scheme 1) and dinuclear complex [(LH) 2 (UO 2 ) 2 (OH) 2 ] (7) (Figure 1) were achieved at room temperature, using a metal/ligand molar ratio 1:2 for the mononuclear complexes and 2:2 for the dinuclear complexes [10,[13][14][15]22]. These products were isolated as analytically pure species via spontaneous precipitation.…”

“…spectra of the ligand and its complexes in DMF showed two or three absorption bands between 260 and 380 nm. These bands are assigned to both charge-transfer transition from the metal to the pà anti-bonding orbital of ligand and spin-allowed p-p* transition of the ligand which is seen at about 300 nm and due to the p-p* transition of the C=N group of the oxime ligand [13][14][15]22]. In these complexes, the HOMO is predominantly the d x2-y2 orbital of the metal and LUMO is the lowest p* orbital of the oxime nitrogen.…”

“…Some of these complexes are soluble, forming thin films, and were investigated as sensitive materials for the detection of organic solvent vapors by utilizing a quartz crystal microbalance and inter-digital capacitors as sensor transducers [16]. Although a large number of vic-dioxime complexes with peripheral donor types such as, MS 2 , MN 4 , MN 2 S 2 , MS 4 , MN 2 S 2 , MN 2 S 2 O 2 , and MO 4 S 2 have been synthesized and characterized, [13][14][15][17][18][19][20][21] alcohol-soluble vic-dioxime transition metal complexes with peripheral reactive functional substituents have not been studied in coordination chemistry.…”

“…So far, great effort has been made in the incorporation of functional groups on the periphery of the vic-dioxime molecule to modify its conformational, optical and electrochemical redox properties. Vic-dioximes, and especially their metal complexes have been widely recognized as being less soluble and even insoluble in a number of organic solvents until recent years [9][10][11][12][13][14][15]. Some of these complexes are soluble, forming thin films, and were investigated as sensitive materials for the detection of organic solvent vapors by utilizing a quartz crystal microbalance and inter-digital capacitors as sensor transducers [16].…”