Coordination properties of 2-aminocyclopentene-1-dithiocarboxylic acid to transition metal ions as studied by ab initio calculations

Abstract

The question of the(N, S) vs. (S, S) coordination mode on M x (ACDA)(2) complexes (ACDA=2-aminocyclopentene-1-dithiocarboxylic acid, M=Ni(2+), Pd(2+), Pt(2+)) was assessed through an extensive ab initio study, using the hybrid B3LYP density functional approach. The (S,S)coordination was found to be the most stable one, with an energy difference of ca. 50 kJ mol(-1) relative to the(N, S) coordination mode. Detailed analysis of the ab initio results indicates that this preference is a result of the combined effect of geometry constraints and electron distribution within the complex.

Highly Sensitive Voltammetric Speciation and Determination of Inorganic Arsenic in Water and Alloy Samples Using Ammonium 2‐Amino‐1‐Cyclopentene‐1‐Dithiocarboxylate

“…Nevertheless, an understanding of the coordination chemistry of ACD with metals is still not well-understood. This stems from the fact that there are different possible coordination sites, such as (N, S) and (S, S), multiple protonation sites, and different tautomeric forms of ACD [67]. When we added 50 g L À1 of surfactants such as Triton X-100 and sodium dodecyl sulfate, they strongly suppressed the cathodic and anodic peaks of As(III), indicating that there is a strongly adsorbed species on the mercury electrode surface.…”

Chlorodiphenyltin(IV) and triphenyltin(IV) complexes of N-alkylated 2-amino-1-cyclopentene-1-carbodithioic acids: synthesis, spectroscopic characterization and X-ray studies

“…Analysis calculated (Found) for C 27 H 29 NS 2 Sn: C,58.91 (58.75);H,5,27 (5.22);N,2.55 (2.49). 1 H NMR (CDCl 3 , d, ppm, 3 J( 1 H, 1 H) and 3 J[ 119 Sn, 1 H] in Hz), 1.28 (d, 6H, H-7,7 0 , (6.3)), 1.85 (q, 2H, H-4, (7.5)), 2.7 (t, 2H, H-3, (7.5)), 2.92 (t, 2H, H-5, (7.3)), 3.69 (m,1H,7.38 (m,9H,4,5),7.77 (m,6H,6,[66.9]), 11.24 (s,1H,NH). 13 C NMR (CDCl 3 ,d,ppm,n J[ 119/117 Sn, 13 C] in Hz), 20.0 (C-4) …”

“…205-207°C. Analysis calculated (Found) for C 21 , H-7,7 0 , (6.3)), 1.89 (q, 2H, H-4, (7.5)), 2.75 (t, 2H, H-3, (7.2)), 2.79 (t, 2H, H-5, (7.2)), 3.79 (m,1H,7.45 (m,6H,4,5),8.09 (m,4H,6,[91.5]), 9.63 (s,1H,NH). 13 C NMR (CDCl 3 ,d,ppm,n J[ 119/117 Sn, 13 C] in Hz), 20.0 (C-4), 23.4 (C-7, 7 0 ), 33.4 (C-3), 33.5 (C-5), 49.8 (C-6), 120.0 (C-1) [40.7], 128.7 (C-c) [86], 129.9 (C-d) [18.1], 135.7 (C-b) [62.6], 143.0 (C-a) [834.6, 798.4], 171.6 (C-2), 188.3 (C-8).…”

“…The bonding in metal complexes takes place either from the amino nitrogen and the deprotonated thiol sulfur (N, S coordination) or from the dithiocarboxylic moiety (S, S coordination). The later pattern can be isobidentate or anisobidentate and this pattern is more frequently observed for Main Group Metals [6]. In recent years, the organotin complexes of the ACDA and its derivatives have been synthesized and characterized by X-ray crystallography [8][9][10][11][12].…”

“…In addition to biological activities, the organotin derivatives of dithiocarbamates are also subjected to thermal and CVD studies [5]. Among the dithiocarbamates, ACDA, 2-amino-1-cyclopentene-1-dithiocarboxylic acid, and its N-and S-alkyl derivatives have received considerable attention due to their good chelating power to the metals [6]. These ligands are interesting because of their potential dual bidentate nature as well as antifungal activity [7].…”