The emerging promise of few-atom metal catalysts has driven the need for developing nanoclusters (NCs) with ultrasmall core size. However, preparation NCs single-digit metallic atoms and atomic precision is a major challenge materials chemists, particularly Ag, where structure such remains unknown. In this study, we developed shape-controlled synthesis strategy based on an isomeric dithiol liga...

All mammalian metallothioneins characterized contain a single polypeptide chain of 61 amino acid residues, among them 20 cysteines providing the ligands for seven metal-binding sites. Native metallothioneins are usually heterogeneous in metal composition, with Zn, Cd, and Cu occurring in varying proportions. However, forms containing only a single metal species, i.e., Zn, Cd, Ni, Co, Hg, Pb, Bi...

[FeFe]-hydrogenases feature a unique active site in which the primary catalytic unit is directly coordinated via a bridging cysteine thiolate to a secondary, redox active [4Fe4S] unit. The goal of this study was to evaluate the impact of a bidentate, redox non-innocent ligand on the electrocatalytic properties of the (μ-S(CH(2))(3)S)Fe(2)(CO)(4)L(2) family of [FeFe]-hydrogenase models as a prox...

Nitrosylation of the chelate-thiolate-containing dinitrosyliron complex (DNIC) [(S(CH(2))(3)S)Fe(NO)(2)](-) triggers nitric oxide (NO) activation to generate the homoleptic nitrosyl {Fe(NO)(2)}(9) DNIC [Fe(NO)(4)](-) (1) made up of two nitroxyls (or two NO anions) attached to a delocalized {Fe(NO)(2)}(9) motif. The significantly longer N3-O3/N4-O4 [1.380(12) and 1.280(12) Å] and Fe1-N3/Fe1-N4 [...

A stable, Ag55 cluster protected with 4-(tert-butyl)benzyl mercaptan (BBSH) was synthesized which exhibits two prominent absorption bands with maxima at 2.25 and 2.81 eV. A molecular ion peak at m/z 11 500 ± 20 in matrix assisted laser desorption ionization mass spectrum (MALDI MS), assigned to Ag55(BBS)31 was observed. Electrospray ionization (ESI MS) shows a prominent trication along with hig...

This review focuses on the impacts of metal-organic interfacial bonding interactions on the charge-transport dynamics involved in molecular junctions as well as organically capped nanoparticles. Whereas mercapto derivatives have been used extensively as the ligands of choice to functionalize metal and nanoparticle surfaces with the formation of metal-thiolate interfacial bonds, recent studies s...

A large library of Cu(II) complexes with mononucleating and dinucleating ligands was synthesized to investigate their potential as catalysts for the catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC). X-ray structure determination for a number of these complexes revealed relatively large Cu···Cu distances and the formation of polymeric species. Comparison of the 3,5-DTBC oxidation rate...

Biological formation and consumption of molecular hydrogen (H2) are catalyzed by hydrogenases, of which three phylogenetically unrelated types are known: [NiFe]-hydrogenases, [FeFe]-hydrogenases, and [Fe]-hydrogenase. We present a crystal structure of [Fe]-hydrogenase at 1.75 angstrom resolution, showing a mononuclear iron coordinated by the sulfur of cysteine 176, two carbon monoxide (CO) mole...

Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxide ligands of the type S-2,3,5,6-Ph4C6H (STPP) and S-2,6-(mesityl)2C6H3 (SHMT = S-hexamethylterphenyl) have been prepared in order to compare their metathesis activity with that of the analogous phenoxide complexes. All thiolate complexes were significantly slower (up to ∼10× slower) for the metathe...

Complexes containing five 4,5-disubstituted-3-mercapto-1,2,4-triazoles and Zn(II), Hg(II) and Cu(I) were synthesized and characterized by standard procedures (elemental analysis; IR, electronic and NMR spectroscopy, conductimetry and TG analysis). Both the thione as well as the thiolate forms of the ligands were evidenced to interact with the metal ions in the prepared complexes. The original m...