N,N′-Dialkyldithiocarbamate chelates of indium(III): alternative synthetic routes and thermodynamics characterization

Abstract

Alternative synthetic routes to prepare N,N H -dialkyldithiocarbamate complexes of indium(III), In(S 2 CNR 2 ) 3 (R CH 3 , C 2 H 5 , n-C 3 H 7 , i-C 3 H 7 , n-C 4 H 9 and i-C 4 H 9 ) from the metallic element and from indium monohalides, InX(X Cl, Br and I) were established. The proposed mechanism of reaction involving InX considering a ligand redistribution reaction of XIn(S 2 C± NR 2 ) 2 initially produced, which could be derived from the insertion of InX into sulfur±sulfur bond of the tetralkylthiuram disul®de. The thermal decomposition of the In(S 2 CNR 2 ) 3 (R CH 3 , C 2 H 5 , n-C 3 H 7 , i-C 3 H 7 , n-C 4 H 9 and i-C 4 H 9 ) compounds was investigated by the thermogravimetric technique, where two pathways were detected, depending on the dialkyldithiocarbamato ligand. The ®rst step leads to indium metal, or alternatively In 2 S 3 , as the ®nal residue for R C 2 H 5 , n-C 3 H 7 , i-C 4 H 9 and for R CH 3 , i-C 3 H 7 , n-C 4 H 9 , respectively. The corresponding standard molar enthalpies of sublimation of all compounds were determined by means of differential scanning calorimetry and methods of estimation. #

Gallium(III) and indium(III) dithiolate complexes: Versatile precursors for metal sulfides

“…The 1 H and 13 C NMR spectra in general show expected resonances with normal splitting features. 12,17,20,21,41 The following trend in the NMR spectra of analogous complexes is quite evident:…”

“…50 The 1 H NMR spectrum of [In(S 2 CNPr i 2 ) 3 ] displays three broad resonances at δ 1⋅50 (Me) and 4⋅00, 5⋅10 (CH) ppm at room temperature. 17 However, below -50°C, spectrum exhibits two doublets of equal intensity for methyl and two septets for methine protons. 51 These doublets and septets coalesce to a single doublet and a septet in the temperature range -50 to 15°C.…”

“…17,62,[68][69][70][71] Tris(xanthate) complexes of indium undergo a single step decomposition leading to the formation of In 2 S 3 . 71 Dithiocarbamate complexes undergo either a single step 17 or two closely spaced steps decomposition in the temperature range 239-389°C.…”

“…Two pathways leading to the formation of either indium metal (R = Et, Pr n , Bu i ) or In 2 S 3 (R = Me, Pr n , Bu i ) have been identified. 17 However, a later TG study showed that [In(S 2 CNEt 2 ) 3 ] yields InS rather than the indium metal. 48 The complex [In(S 2 CNBz 2 ) 3 ] on pyrolysis releases CS 2 and benzyl moieties in the gas phase leaving behind bulk In 2 S 3 .…”

Synthesis and characterization of mixed ligand catecholato-bis (diamine-mono-dithiocarbamato) vanadium (IV) complexes

“…1 and 2, respectively. It was reported that the protons for >CH 2 group has chemical shift in the range δ = 1.43-1.54 ppm (Oliveira et al 1999). The peak in the region 3.82-3.64 ppm for the protons of -NH 2 group was ascribed by Onwudiwe (2011).…”