Synthesis, structural, DFT calculations and Hirshfeld surface analysis of (N-butyl-N-(4-fluorobenzyl)dithiocarbamato-S,S')-(thiocyanato-N)(triphenylphosphine)nickel(II) and preparation of nickel sulfide from nickel(II) dithiocarbamate

Abstract

<p></p> <p>Bis(N-butyl-N-(4-fluorobenzyl)dithiocarbamato-S,S')nickel(II) (<b>1</b>) and (N-butyl-N-(4-fluorobenzyl)dithiocarbamato-S,S')(thiocyanato-N)(triphenylphosphine)-nickel(II) (<b>2</b>) have been prepared. Both the complexes have been characterized by elemental analyses, IR, electronic and ¹H and ¹³C NMR spectroscopy. Single crystal X-ray analysis of complex <b>2</b> showed a distorted square planar configuration around the nickel atom due to steric effect of the triphenylphosphine and the bidentate chelation by two sulfur atoms of the dithiocarbamate ligand. UV-Vis spectral data of <b>1</b> and <b>2</b> are consistent with the formation of square planar nickel(II) complexes. Hirshfeld surface analysis was also carried out to provide qualitative and quantitative insights into the intermolecular interactions in <b>2</b>. Molecular electrostatic potential surface map reveals that the negative charge is delocalized over S atoms of NCS₂ and the positive charge is localized over N atom of NCS₂ group. This indicates the considerable double bond character of the C-N (thioureide) bond. Nickel sulfide nanoparticles have been prepared from complex <b>1</b> and characterized using PXRD, EDS, UV-DRS, and SEM. EDS analysis confirm the formation of nickel sulfide.</p