We report the total structure of Au38(SC2H4Ph)24 nanoparticles determined by single crystal X-ray crystallography. This nanoparticle is based upon a face-fused Au23 biicosahedral core, which further capped three monomeric Au(SR)2 staples at waist rod and six dimeric with on top icosahedron other bottom icosahedron. The Au2(SR)3 are arranged in staggered configuration, Au38S24 framework has C3 rotation axis.

We report a solution-phase conversion process of the [Au25(SCH2CH2Ph)18]− anionic cluster into charge neutral [Au25(SCH2CH2Ph)18]0 via air oxidation. The one-electron loss Au25− and to Au250 is surprise in light chemical inertness gold nanoparticles. In contrast with crystal structure anion Au25−, which exhibits apparent structural distortions Au25S18 framework, such are not observed cluster. effect also manifested optical absorption spectra clusters. Given only recently reported parent...

Recent work towards the production of hydrogen via reduction protons is described. Most systems examined in this perspective use a molecular chromophore for harvesting visible light, catalyst, which reduced by excited (or reduced) chromophore, and finally sacrificial electron source to oxidatively or reductively quench chromophore. The catalyst then responsible resulting evolution. Relevant mechanistic on topic also discussed.

This article reports on recent advances in the area of catalyst regeneration copper mediated atom transfer radical addition (ATRA) and cyclization (ATRC) reactions using free‐radical diazo initiators as reducing agents. The role agent both processes is to continuously regenerate activator (copper(I) complex) from deactivator (copper(II) complex). As a result, single adducts ATRA ATRC can be synthesized very low concentrations catalysts (5–100 pm). Previously, efficient catalysis for required...

We previously reported a size-focusing conversion of polydisperse gold nanoparticles capped by phosphine into monodisperse [Au(25)(PPh(3))(10)(SC(2)H(4)Ph)(5)Cl(2)](2+) nanoclusters in the presence phenylethylthiol. Herein, we have determined crystal structure and also identified an important side-product-a Au(I) complex formed size focusing process. The cluster features vertex-sharing bi-icosahedral core, resembling rod. formula is to be [Au(2)(PPh(3))(2)(SC(2)H(4)Ph)](+) electrospray...

Highly efficient atom transfer radical addition of polyhalogenated compounds to alkenes catalyzed by copper(I/II) complexes with tris(2-pyridylmethyl)amine in the presence a initiator [2,2'-azobis(2-methylpropionitrile)] was reported.

Abstract The synthesis, characterization and exceptional activity of Cu I (TPMA)Br [TPMA = tris(2‐pyridylmethyl)amine] [Cu II (TPMA)Br][Br] complexes in ATRA reactions polybrominated compounds to alkenes the presence reducing agent (AIBN) was reported. (TPMA)Br][Br], conjunction with AIBN, effectively catalyzed CBr 4 CHBr 3 concentrations between 5 100 ppm, which is lowest number achieved copper‐mediated ATRA. molecular structure indicated that complex pseudo‐pentacoordinate solid state due...

In recent years, copper-catalyzed atom transfer radical addition (ATRA) has emerged as a viable organic procedure for the formation of carbon-carbon bonds starting from alkyl halides and alkenes. Studies have primarily focused on use free-radical initiators to regenerate copper(I) complex or activator in situ. Although these led significant decrease amount metal catalyst, they were much less effective highly active alkenes that readily undergo polymerization. this study, non-radical reducing...

Homogeneous light-driven systems employing molecular molybdenum catalysts for hydrogen production are described. The specific Mo complexes studied six-coordinate bis(benzenedithiolate) derivatives having two additional isocyanide or phosphine ligands to complete the coordination sphere. Each of possesses a trigonal prismatic geometry. were investigated as proton reduction in presence [Ru(bpy)3](2+), ascorbic acid, and visible light. Over 500 TON obtained over 24 h. Electrocatalysis occurs...

Copper(I) complexes with the tris(2-pyridylmethyl)amine (TPMA) ligand were synthesized and characterized to examine effect of counteranions (Br(-), ClO(4)(-), BPh(4)(-)), as well auxiliary ligands (CH(3)CN, 4,4'-dipyridyl, PPh(3)) on molecular structures in both solid state solution. Partial dissociation one pyridyl arms TPMA was not observed when small such CH(3)CN or Br(-) coordinated copper(I), but found occur larger ones PPh(3) 4,4'-dipyridyl. All adopt a distorted tetrahedral geometry,...

In this article, we focus on the evaluation of tris[2-(dimethylamino)ethyl]amine (Me6TREN) ligand in copper catalyzed ATRA presence free-radical diazo initiator AIBN (2,2′-azobis(2-methylpropionitrile)). The addition carbon tetrachloride to 1-hexene, 1-octene and cis-cyclooctene proceeded efficiently yield 89, 85 85% monoadduct, respectively, using catalyst alkene ratio 1 : 2500. For alkenes that readily undergo free radical polymerization, such as methyl acrylate, loadings high 0.4 mol-%...

A series of chalcogenorhodamine dyes with oxygen, sulfur, and selenium atoms in the xanthylium core was synthesized used as chromophores for solar hydrogen production a platinized TiO2 catalyst. Solutions containing selenorhodamine dye generate more [181 turnover numbers (TONs) respect to chromophore] than its sulfur (30 TONs) oxygen (20 counterparts. This differs from previous work incorporating these into dye-sensitized cells (DSSCs), where oxygen- selenium-containing species perform...

Kinetic and mechanistic studies of atom transfer radical addition (ATRA) catalyzed by copper complexes with tris(2-pyridylmethyl)amine (TPMA) ligand were reported. In solution, the halide anions found to strongly coordinate [Cu(I)(TPMA)](+) cations, as confirmed kinetic, cyclic voltammetry, conductivity measurements. The equilibrium constant for (K(ATRA) = k(a)/k(d)) utilizing benzyl thiocyanate was determined be approximately 6 times larger Cu(I)(TPMA)BPh(4) ((1.6 ± 0.2) × 10(-7)) than...

We demonstrate the synthesis and characterization of a new class late-transition-metal-aluminum heterobimetallic complexes via novel synthetic pathway. Complexes this type are exceedingly rare. Joint experimental theoretical data sheds light on electronic effect ligands containing aluminum moieties late-transition-metal complexes.

A series of seven molybdenum(III) complexes with the general formula [Mo(diimine)Cl4]− were synthesized and characterized by X-ray diffraction, IR, cyclic voltammetry (CV), UV–vis. The discovered to be highly solvatochromic, showing shifts in λmax between ∼120 170 nm solvents ranging from water acetone. Varying substituents on diimine ligand influenced absorption energy such that electron-withdrawing groups induced a red shift while electron-donating exhibited opposite effect. surprisingly...

Abstract Slow initiation from the bridgehead radical in atom transfer polymerization (ATRP) reactions initiated by 9‐bromoanthracene photodimers leads to polymers' products possessing high PDI values and higher than expected $\overline M _{\rm n}$ values. We report here effects of changing ligand N , ′, ″, ″‐pentamethyldiethylenetriamine (PMDETA) highly active tris[2‐(dimethylamino)ethyl]amine (Me 6 TREN) or tris[(2‐pyridyl)methyl]amine (TPMA) an attempt push initial equilibrium further...

With the mounting need for clean and renewable energy, catalysts hydrogen production based on earth abundant elements are of great interest. Herein, we describe synthesis, characterization, catalytic activity two nickel complexes pyridinediimine ligand that possess basic nitrogen moieties pyridine imidazole could potentially serve as pendent bases to enhance catalysis. Although these ligands have previously been reported be complexed some metal ions, they not applied nickel. The complex with...

In the title compound, [Cu(C 14 H 12 N 2 ) ]C 24 20 B·CH Cl , Cu I is chelated by two 2,9-dimethyl-1,10-phenanthroline (2,9-Me phen) ligands, in a distorted tetrahedral coordination geometry. The average Cu—N bond length 2.032 Å, and interligand dihedral angle 77.60 (6)°. complexes form π–π stacking interactions between 2,9-Me phen with perpendicular interplanar separation of 3.652 (5) Å.

We demonstrate the synthesis and characterization of regioisomeric late transition metal‐aluminum heterobimetallic complexes containing 3‐ 4‐oxypyridine ligands which bridge between aluminum metal center (Rh or Ir). Combined experimental theoretical data allow for direct comparison electronic effect two different aluminum‐containing on center. In combination with regarding previously reported 2‐oxypyridine bridged systems, we report a measurable decrease in ligand donor power as...