Transition‐Metal Thiolates: From Molecular Fragments of Sulfidic Solids to Models for Active Centers in Biomolecules

Abstract

Thiolates are presently a subject of great interest in the chemistry of complexes involving transition-metal elements and soft ligands. The manifold electronic and steric capabilities offered by the monodentate ligands RS" and the bidentate chelate ligands "SRSO have been used to stabilize a broad spectrum of mononuclear, oligomeric, and polymeric complexes with new and remarkable structures and properties. Impetus has especially been provided by the synthesis of polynuclear cagelike homo-and heteroleptic metal-sulfur frameworks, which can often be regarded as "molecular fragments" of the structures of inorganic sulfides. Thiolates and mixed sulfide-thiolates of the late open-and closed-shell 3d metals (Fe, Co, Ni, Cu, Zn) and some of their homologues (Au, Cd, Hg), as well as of Mo, are of particular importance as model complexes for biologically important metal centers coordinated by sulfur. They have played an important role in increasing our understanding of the structure, bonding, and function of the reactive centers in ferredoxins, rubredoxins, nitrogenases, blue copper proteins, metallothioneins, and antiarthritic drugs.

Synthesis of palladium and palladium sulfide nanocrystals via thermolysis of a Pd–thiolate cluster

“…According to theoretical investigation [50], the Pd-S π bonding orbitals distributing throughout the palladium ring play a pivotal role in constructing and stabilizing the characteristic tiara-like structure. Such atomic arrangement has a triple-layered tiara-like structure and has also been found in other analogous [Pd(SR) 2 [8][9][10].…”

“…Transition metal thiolates play important roles in helping us understand the biological processes and in the progress of coordination chemistry [1,2]. Thiolate ligands (SR) could bond with metal atoms in different coordination modes, terminal, μ 2 -bridging or μ 3 -bridging modes [3][4][5].…”

“…Palladium nanostructures of different sizes and morphologies play crucial roles in organic catalysis [31][32][33][34][35][36] 2 was dissolved in 8 mL acetate acid and gave a bright yellow solution. Then, 8 mL DMSO and 8 mL EG were added under stirring.…”

Synthesis and Characterization of [Zn(SEt)Et]10, Formed via Insertion of Sulfur into Zn-C Bonds: A New Class of Wurtzite-like Cluster Framework

“…Metal thiolate compounds exhibit a rich and interesting structural chemistry that has been studied extensively. 14 -These complexes are of scientific and technological interest as a result of their structural similarity to metalloproteins, metallothioneins 7 and the possibility that they can be used as precursors for the formation of binary metal sulfides. 8 …”

Crystal structure of 1-(4-fluorophenyl)-N-(5-((triphenylstannyl)thio)thiophen-2-yl)methanimine, C27H20FN3S2Sn

“…Metal thiolato complexes have been extensively studied because of their ability to adopt various nuclearities and their relevance in biology, since they form the inorganic part of the biologically active centers of some metalloproteins and enzymes [5,6]. Recently, attention has been paid to the coordination chemistry of heterocyclic thiol/thione donors, which can give potential access to new complexes with unusual structures and reactivities [7].…”