Metallkomplexe naphthyl‐substituierter Thioharnstoffderivate

Abstract

Inhaltsübersicht. Es wurden das Thioharnstoffderivat N,N-Diethyl-NЈ-2-naphthoylthioharnstoff (1) und drei N-(Dialkylaminothiocarbonyl)-NЈ-(1-naphthyl)-arylamidine (2-4) synthetisiert und mit diesen Cu II -, Ni II -und Pd II -Komplexe dargestellt. Die röntgenstrukturanalytischen Untersuchungen zeigen, daß 1 mit Cu II und Ni II unter Deprotonierung neutrale Bischelate von nahezu quadratischplanarer Koordination mit einer cis-Anordnung der O-und S-Liga-Abstract. The thiourea derivative N,N-diethyl-NЈ-2-naphthoylthiourea (1) and three N-(dialkylaminothiocarbonyl)-NЈ-(1-naphthyl)arylamidines (2-4) have been synthesized and Cu II -, Ni II -and Pd IIcomplexes of them have been prepared. According to the X-ray structure analyses 1 with Cu II and Ni II under deprotonation forms neutral bis-chelates of nearly square-planar coordination with a cis arrangement of the O and S ligator atoms. Using their N and S atoms in 1,3 position as ligators, 2-4 in deprotonated form coordi- EinleitungBei 2:1-Acylthioharnstoffmetallchelaten wird in der Regel cis-Koordination beobachtet. Bisher ist erst ein davon abweichender Ausnahmefall, nämlich das Naphthylgruppentragende trans -Bis(N,N-dibutyl-NЈ-1-naphthoylthioureato)platin(II) [1, 2], dargestellt und strukturell charakterisiert worden. Andererseits haben sich naphthylsubstituierte Liganden, die Schwefel-und Stickstoffatome als potentielle Ligatoratome enthalten, in jüngster Zeit für fluoreszenzanalytische Bestimmungen von umweltchemisch relevanten Schwermetallen [3, 4] und auch für die Anionenanalytik von Carbonat, Hydrogencarbonat und Hydrogenphosphat [5] als geeignet erwiesen. 1051 toratome bildet. 2-4 binden in deprotonierter Form über ihre Nund S-Atome in 1,3-Stellung an Cu II und Pd II zu neutralen Bischelaten Ϫ im Fall von Cu II mit verzerrt tetraedrischer Koordination. Pd II wird quadratisch-planar koordiniert und hat, offenbar aufgrund des sterischen Einflusses der 1-Naphthylgruppen, eine trans-Anordnung der N-und S-Ligatoratome.nate to Cu II and Pd II as neutral bis-chelates, in the case of Cu II with a distorted tetrahedral coordination. Pd II is coordinated square planar and has, probably due to the spatial influence of the 1-naphthyl groups, a trans arrangement of the N and S ligator atoms.

Syntheses, Structures, and Biological Activity of NiII, PdII, and PtII Complexes with New Tetradentate Benzamidine Ligands

“…The benzamidine unit does not bind to the aromatic amine, but to the benzylamine and the azomethine bond is formed with the nitrogen atom of the aromatic amine. The C8-N7 bond length of 1.284(2) Å is clearly within the range of carbon-nitrogen double bonds, [4,17] which additionally confirms the formation of an azomethine group with the aromatic Morph . [14] Hydrogen atoms bonded on carbon atoms are omitted for clarity.…”

“…Despite the fact that bidentate N-(dialkylthiocarbamoyl)-benzamidines (1) (Scheme 1) are well known chelators, which form stable complexes with most transition metal ions, [1][2][3][4] the coordination chemistry of tri-and tetradentate benzamidines is almost unexplored. [5][6][7][8] Hitherto, only a few tridentate benzamidines, [5][6][7][8] and two tetradentate benzamidines with an S,N,N,S donor set have been reported.…”

ReVO and ReVNPh complexes with pentadentate benzamidines – Synthesis, structural characterization and DFT evaluation of isomeric complexes

“…Very strong absorptions around 1720 cm -1 are assigned to ν C=O vibrations, which are well separated from the strong absorptions of the ν C=N stretches in the 1616 cm -1 region [21][22][23][24]. The 1 H NMR spectra of H 3 L are characterized by two singlets around 3.45 ppm and 4.00 ppm, which are assigned to the methylene protons of NCH 2 CO and PhCH 2 N, respectively.…”

Crystal structure of cis-copper(II) complex with N-(di-n-propylcarbamothioyl)cyclohexanecarboxamide ligand

“…Thiourea derivative ligands are tend to coordinate to both transition group and main group metal ions via both sulfur and oxygen providing a multitude of bonding possibilities [11][12][13]. Copper(II) complexes of acyl thiourea ligands have been described repeatedly in the literature with regard to their synthesis and general characterization [14][15][16] and molecular structures [17][18][19][20]. These copper(II) complexes are in every case nearly square-planar neutral bis chelates with a cis arrangement of the ligands around the copper atom.…”