Solvothermal preparation of nano cobalt sulfide from tris (cyclohexylpiperazinedithiocarbamato)cobalt(III) and characterization, single crystal X-ray crystal structure of the precursor

Abstract

Solvothermal formation of CoS nano particles is reported with a cobalt(III) dithiocarbamate as a single source precursor. Morphology and composition of the nano product have been characterized by PXRD and EDX analysis. Four unsymmetrically substituted tris cobalt(III) compounds, [Co(chmdtc)₃] (1), [Co(chedtc)₃] (2), [Co(achdtc)₃] (3), and [Co(chpdtc)₃] (4) (where chmdtc = cyclohexylmethylcarbodithioate, chedtc = cyclohexylethylcarbodithioate, achdtc = allylcyclohexylcarbodithioate and chpdtc = cyclohexylpiperazinecarbodithioate) were synthesized and characterized. Compounds (1)– (4) show bands at 634, 642, 635, and 643 nm respectively, due to d-d transitions. One electron quasi reversible reductions due to Co(III)/Co(II) redox process are observed in CV. In the ¹³C NMR spectra of the complexes, the thioureide (N¹³CS₂) carbons resonate between 203.8 and 205.7 ppm. The observed deshielding of the –CH₂ protons in ¹H NMR of the compounds is attributed to the shift of electron density on the sulfur (or the metal) through the thioureide π system. TGA supported the proposed formulas of the compounds. Single crystal X-ray structure of [Co(chpdtc)₃] (4) shows that the cobalt is in a distorted octahedral environment. Bond Valence Sum (BVS) calculations confirmed the formal oxidation state of cobalt as +3.

Graphical Abstract

Keywords:

• Dithiocarbamate
• thioureide
• solvothermal
• nano cobalt sulfide
• single crystal X-ray crystal structure

Disclosure statement

No potential conflict of interest was reported by the author(s).