Synthesis and spectroscopic Investigation of Mixed‐Ligand Copper Chelates containing 2‐hydroxyaryloximes and N‐disubstituted dithiocarbamates. Crystal and molecular structure of trans‐bis[propanone, 1‐(2‐hydroxy‐phenyl)oximato] copper(II)

Abstract

A series of mixed-ligand copper(I1) chelates containing the anion of 2-hydroxyaryloxime(oxime) and N,N-disubstituted dithiocarbamate(dtc), [Cu(dtc)(oxime)], was prepared and characterised. The spectra (IR, ESR, electronic excitation) indicate that the CuNOS2 chromophore attains square planar geometry. The ESR observables suggest appreciable covalency. In the case of [Cu(Et2dtc)(oxime)] chelates, however, the observed data suggest distortion from square planar arrangement to a square pyramidal, indicative of a possible dimerism.In addition, the structure of the trans-bis[propanone, 1-(2-hydroxyphenyl)-oximato]copper(II), Cu(CgH10N02)2 was determined by X-ray piffraction (mon?clinic, space gro!p P21/n, a = 12.072 (7) A, b = 5.204(2) A, c = 13.571(6) A, p = 103.72(1)", Z = 2). The molecule consists of discrete C~( p p o x )~ monomeric units, where the Cu atom is in the equatorial plane bonded to two nitrogen ?toms and two oxygen at distances of 1.949(2) and 1.882 (2) A, respectively. Synthese und spektroskopische Untersuchung von gemischten Kupfer-Chelaten von 2-Hydroxyaryloxim und N-substituierten Dithiocarbamaten. Kris t allund Mole kulars t ru kt ur von trans-Bis[propanon, 1-(2-hydroxyphenyl)-oximato]Kupfer(II) Inhaltsiibersicht. Kupfer(I1) Chelate mit den Anionen von 2-Hydroxyaryloxim (oxime) und N,N-disubstituieren Dithiocarbamaten (dtc), [Cu(dtc)(oxime)], wurden dargestellt und charakterisiert. Die Spektren (IR, ESR, elektronische Anregung) zeigen, daB die chromophore Einheit CuNOSz quadratisch planar ist. ESR-Beobachtungen indizieren einen starken covalenten Charakter. Bei den Chelaten [Cu(Et2dtc)(oxime)], deuten die experimentellen Daten auf eine Verzerrung zu einer quadratischen Pyramide, was moglicherweise auf eine Dimerisierung hinweist. Die Struktur des trans-bis[propanon,l-(2-hydroxyphenyl)oximato]Kupfer(II), Cu(CgH10N02)2, wurde rontgenographisth bestimmt (Fonoklin, R a u m p p p e P~& I , a = 12.072(7) A, b = 5.204(2) A, c = 13.571(6) A, p= 103.72(1)", Z = 2). Das Molekul besteht aus isolierten monomeren Cu(ppox)z-Einheiten, in denen das Cu Atom in der aquatorialen Ebene liegt und an zwei Stickstoff-und zwei Sauerstoffatomen in Abstanden von 1.949(2) bzw. 1.882(2) gebunden ist. 4 [Cu(Pipdtc)(ppox)] 5 [Cu(Pipdtc)(bpox)] 6 [Cu(Pipdtc)(opox)] 7 [Cu(Etzdtc)(saox)] 8 [Cu(Etzdtc)(apox)] 9 [Cu(Etzdtc)(mpox) 10 [C~(Etzdtc)(ppox)] 11 [C~(EtZdt~)(bpox)] 12 [C~(Etzdt~)(opo~)] 13 [Cu(Benzzdtc)( saox)] 14 [Cu( Benzzdtc)( apox)] 15 [ Cu( B enz,dtc) (mpox)] 16 [Cu(Benzzdtc)(ppox)] 17 [Cu(Benzzdtc)(bpox)] 18 [Cu(Benzzdtc)(opox)]

Synthesis and Characterization of Mixed-Ligand Nickel(II) Chelates of β-Diones and α-Diimines. Crystal and Molecular Structure of [Ni(ncup)2Etacet]ClO4

“…Physical measurements and determination. Magnetic susceptibility, stoichiometry and spectroscopic measurements were performed employing apparatus and techniques that have been previously described [9]. Electric conductance measurements were carried out with a WTW model LF 530 conductivity outfit and a type C cell, which had a cell constant of 0.996.…”

Συνθεση Και Μελετη Μικτων Ενωσεων Συναρμογης Μερικων Δισθενων Μεταβατι Κων Στοιχειων Με 2-Υδροξυοξιμες Β-Κετοενολες Και Αζωτουχες Βασεις Ως Ligands

“…Μελέτες της κρυσταλλικής και μοριακής ενώσεων του τύπου αυτού με νικέλιο[62,[64][65][66], παλλάδιο[67,68] και χαλκό[69][70][71] απέδειξαν ότι η γεωμετρία τους είναι επίπεδητετραγωνική με trans διαμόρφωση, όπου τα άτομα μετάλλου, αζώτου και διαμόρφωση. Η ισορροπία μεταξύ κετονικής και ενολικής μορφής αποδεικνύεται με μελέτες πολαρογραφικές[80],,IR [82,83] και κυρίως NMR [79,84].…”