Silver(I) and Gold(I) Monothiocarbonate Complexes: Synthesis, Structure, Luminescence

Abstract

The monothiocarbonate ligand, [S(O)COR]−, is unusual and rare regarding its use in the formation of coordination compounds. Here, we report the synthesis and structures of the silver(I) and gold(I) monothiocarbonate complexes, [{Ag4(SC(O)OiPr)2(2,2′-bpy)4}(PF6)2]n (1) and [Au2{S(O)COiPr}2(dppe)]n (2), respectively. Both complexes are coordination polymers, with 1 being cationic and 2 neutral. The uniqueness of the ligand is that it is monoanionic and contains both a ‘hard’ O-donor ligand and a ‘soft’ S-donor ligand in a O-C-S manifold with, in principle, electron delocalization across the three atoms. However, for both complexes 1 and 2, it was found that the binding occurred exclusively through the S-donor atom, while the C=O portion remained dangling and was not involved in bonding. This bonding mode departs significantly from the symmetrical S-C-S type ligand such as dithiocarbamates. The structures were analysed and confirmed by NMR and X-ray crystallography.

Cd(II) and Pd(II) Mixed Ligand Complexes of Dithiocarbamate and Tertiary Phosphine Ligands—Spectroscopic, Anti-Microbial, and Computational Studies

“…At the same time, their ability to adopt resonance hybrids allows for stabilizing metals in both high and low oxidation states [16][17][18][19][20][21][22][23][24][25][26]. Over the past decade, the development of dithiocarbamate chemistry has continued unabated with applications in areas including novel inorganic drugs, capping agents for nano-engineered surfaces and other nanomaterials, including quantum dots, and the rational construction of well-defined complex molecular structures [17][18][19][20][21][22][23][24][25][26].…”

“…Howe dithiocarbamate ligands and their complexes have drawn considerable interest of their intriguing biological characteristics [15][16][17]. Moreover, they have applic areas as diverse as medicine, agriculture, biological imaging, and materials scien are extremely versatile ligands, forming stable complexes with all the transition along with the lanthanides, the actinides, and a majority of the p-block element same time, their ability to adopt resonance hybrids allows for stabilizing metal high and low oxidation states [16][17][18][19][20][21][22][23][24][25][26]. Over the past decade, the develop dithiocarbamate chemistry has continued unabated with applications in areas in novel inorganic drugs, capping agents for nano-engineered surfaces an nanomaterials, including quantum dots, and the rational construction of well complex molecular structures [17][18][19][20][21][22][23][24][25][26].…”