Mixed-ligand nickel(II) and copper(II) complexes of tridentate ONS and NNS ligands derived from S-alkyldithiocarbazates with the saccharinate ion as a co-ligand

Ali, Mohammad Akbar, Mirza, Aminul Huq, Ting, Wong Yok, Hamid, Malai Haniti S. A., Bernhardt, Paul V. and Butcher, Ray J. (2012) Mixed-ligand nickel(II) and copper(II) complexes of tridentate ONS and NNS ligands derived from S-alkyldithiocarbazates with the saccharinate ion as a co-ligand. Polyhedron, 48 1: 167-173. doi:10.1016/j.poly.2012.08.069


Author Ali, Mohammad Akbar
Mirza, Aminul Huq
Ting, Wong Yok
Hamid, Malai Haniti S. A.
Bernhardt, Paul V.
Butcher, Ray J.
Title Mixed-ligand nickel(II) and copper(II) complexes of tridentate ONS and NNS ligands derived from S-alkyldithiocarbazates with the saccharinate ion as a co-ligand
Journal name Polyhedron   Check publisher's open access policy
ISSN 0277-5387
1873-3719
Publication date 2012-11
Sub-type Article (original research)
DOI 10.1016/j.poly.2012.08.069
Volume 48
Issue 1
Start page 167
End page 173
Total pages 7
Place of publication Oxford United Kingdom
Publisher Pergamon
Collection year 2013
Language eng
Formatted abstract
New mixed-ligand complexes of the general formula, [M(L)(sac)] (M = Ni2+, Cu2+; L- = anionic forms of the salicylaldehyde Schiff base of N-methyl-S-methyldithiocarbazate (Hsalsme), the salicylaldehyde 2-N-methyl-3-thiosemicarbazone (Hsaltsc), the methylpyruvate Schiff base of S-methyldithiocarbazate (Hmpsme) and the quinoline-2-methoxycarboxaldehyde Schiff base of S-methyldithiocarbazate (quinolsme); sac- = the saccharinate anion) have been synthesized and characterized by IR, electronic and magnetic susceptibility measurements. Magnetic and spectroscopic data support a distorted square-planar structure for the [M(ONS/NNS)(sac)] complexes (ONS/NNS = salsme, saltsc, mpsme or quinolsme).

The structures of Hsalsme, [Cu(salsme)sac] and [Cu(quinolsme)sac] have been determined by X-ray diffraction. The complex, [Cu(salsme)sac] has a distorted square-planar structure with the Schiff base acting as a uninegatively charged ONS tridentate chelating agent coordinating the copper(II) ion via the phenolic oxygen, the azomethine nitrogen and the thione sulfur atoms, the fourth coordination position being occupied by an N-bonded saccharinate anion.

The reaction of [Cu(sac)4(H2O)2·2H2O with the 2-quinolinecarboxaldehyde Schiff base of S-methyldithiocarbazate (Hqsme) in boiling methanol does not lead to the formation of the expected mixed-ligand complex, [Cu(qsme)(sac)], but an unusual substitution of the hydrogen atom attached to the azomethine carbon by a methoxy group occurs with the concomitant formation of the complex [Cu(quinolsme)(sac)] of a new ligand (quinolsme = anionic form of the quinolone-2-methoxycarboxaldehyde Schiff base of S-methyldithiocarbazate). An X-ray crystal structure determination reveals that the Schiff base Hquinolsme is coordinated to the copper(II) ion in its deprotonated thiolate form as an NNS tridentate chelating agent and the fourth coordination position of the square-planar copper(II) centre is occupied by an N-bonded saccharinate anion.
Keyword Mixed-ligand nickel(II) and copper(II) complexes containing the saccharinate ion
Schiff bases
Dithiocarbazate ligands
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2013 Collection
School of Chemistry and Molecular Biosciences
 
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