Abstract Revealing structural isomerism in nanoparticles using single-crystal X-ray crystallography remains a largely unresolved task, although it has been theoretically predicted with some experimental clues. Here we report pair of isomers, Au 38T and 38Q , as evidenced electrospray ionization mass spectrometry, photoelectron spectroscopy, thermogravimetric analysis indisputable crystallography. The two isomers show different optical catalytic properties, differences stability. In addition,...

Alloy nanoparticles with atomic monodispersity is of importance for some fundamental research (e.g., the investigation active sites). However, controlled preparation alloy has long been a major challenge. Herein, first time unique method, antigalvanic reduction (AGR), introduced to synthesize atomically monodisperse Au25Ag2(SC2H4Ph)18 in high yield (89%) within 2 min. Interestingly, two silver atoms do not replace gold precursor particle Au25(SC2H4Ph)18 but collocate on Au25, which was...

The NH2 group in primary allylic amines was substituted directly by sulfinate salts with excellent regio- and stereoselectivities. In the presence of 0.1 mol % [Pd(allyl)Cl]2, 0.4 1,4-bis(diphenylphosphino)butane (dppb), excess boric acid, a range α-unbranched were smoothly sodium sulfinates an α-selective fashion to give structurally diverse sulfones good yields exclusive E selectivity. Replacing dppb 1,1′-bi-2-naphthol (BINOL) allowed unsymmetric α-chiral be transformed into corresponding...

Abstract Metal nanoclusters have recently attracted extensive interest not only for fundamental scientific research, but also practical applications. For it is of major importance to explore the internal structure and crystallographic arrangement. Herein, we synthesize a gold nanocluster whose composition determined be Au 60 S 6 (SCH 2 Ph) 36 by using electrospray ionization mass spectrometry single crystal X-ray crystallography (SCXC). SCXC reveals that consists fcc-like 20 kernel protected...

The 18-electron shell closure structure of Au nanoclusters protected by thiol ligands has not been reported until now. Herein, we synthesize a novel nanocluster bearing the same gold atom number but different thiolate as another structurally resolved Au44(TBBT)28 (TBBTH = 4-tert-butylbenzenelthiol). new cluster was determined to be Au44(2,4-DMBT)26 (2,4-DMBTH 2,4-dimethylbenzenethiol) using multiple techniques, including mass spectrometry and single crystal X-ray crystallography (SCXC)....

Atomically precise metal nanoclusters have received tremendous attention due to their unique structures and properties. Although synthetic approaches this kind of nanomaterial been well developed, methods toward precision functionalization the as-synthesized are extremely limited, hindering interfacial modification related performance improvement. Herein, an amidation strategy has developed for Au11 nanocluster based on preorganized nitrogen sites. The did not change number gold atoms in...

The investigation of chirality at the nanoscale is important to bridge gap between molecular and macroscopic chirality. Atomically precise metal nanoclusters provide an ideal platform for this research, while their enantiopure preparation poses a challenge. Here, we describe efficient approach via asymmetric transformation, that is, achiral Au23(SC6H11)16 are converted into chiral Au24(L)2(SC6H11)16 by inducer phosphoramidite (L). Two enantiomers obtained crystal structures reveal...

The induced structural transformation provides an efficient way to precisely modulate the fine structures and corresponding performance of gold nanoclusters, thus constituting one important research topics in cluster chemistry. However, driving forces mechanisms these processes are still ambiguous many cases, limiting further applications. In this work, based on unique coordination mode pincer ligand-stabilized nanocluster Au8(PNP)4, we revealed site-recognition mechanism for transformations...

An unprecedented catalyst-free alkylation of sulfinic acids with sulfonamides has been developed via sp(3) C-N bond cleavage at room temperature. In the absence external catalysts and additives, a wide variety N-benzylic N-allylic couple to give structurally diversified sulfones in moderate excellent yields. Furthermore, reaction N-(2-acyl)allylic provides convenient access trisubstituted allyl exclusive Z selectivity.

The acid-catalyzed benzylic and allylic alkylation of protic nucleophiles is fundamentally important for the formation carbon-carbon carbon-heteroatom bonds, it a formidable challenge amine derivatives to be used as alkylating agents. Herein we report highly efficient carbon sulfur with sulfonamides through double Lewis acid catalyzed cleavage sp(3) carbon-nitrogen bonds at room temperature. In presence catalytic amount inexpensive ZnCl(2)-TMSCl (TMSCl: chlorotrimethylsilane), 1,3-diketones,...

A novel nanocluster Au₄₄(SC₂H₄Ph)₃₂ exhibiting high catalytic activity at low-temperature was synthesized by an oxidation–decomposition–recombination (ODR) process.

Structural isomerization is an important concept in organic chemistry and it recently found to be applicable thiolated gold nanoparticles. However, the best of our knowledge, with kernel structure cluster changed while maintaining fcc packing was not previously found. Here, we report such a structural by synthesizing novel nanocluster solving its atomic structure. The as-obtained Au52(PET)32 (PET = phenylethanethiolate) has completely same Au/S molar ratio as well-known Au52(TBBT)32 (TBBT...

A palladium-catalyzed oxidative tandem process of enallenols was accomplished within a homogeneous/heterogeneous catalysis manifold, setting the stage for highly chemodivergent and diastereoselective synthesis γ-lactones γ-lactams under mild conditions.

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTPeeling the Core–Shell Au25 Nanocluster by Reverse Ligand-ExchangeMan-Bo Li†, Shi-Kai Tian‡, Zhikun Wu*†, and Rongchao Jin*§View Author Information† Key Laboratory of Materials Physics, Anhui Nanomaterials Nanotechnology, Institute Solid State Chinese Academy Sciences (CAS), Hefei, 230031, China‡ Department Chemistry, University Science Technology China, 230026, China§ Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United...

Tuning the nanoclusters’ compositions and structures is critical for performance improvement of nanoclusters. Herein, a well‐known Au 25 ( SCH 2 CH Ph ) 18 (Au short) nanocluster has been transformed to rare cadmium doped gold [ 13 Cd PPh 3 6 SC H 4 NO ] 26 5 by peeling doping. Although exhibits no catalytic activity toward A ‐coupling reaction under investigated conditions, novel shows high activity, as well good recyclability substrate tolerance same reaction. The attributed cooperation...

ConspectusPalladium-catalyzed oxidations involving cascade processes provide a versatile platform for streamlined conversion of simple feedstocks into functional molecules with high atom and step economy. However, the achievement palladium efficiency selectivity in Pd-catalyzed oxidative reactions is still challenging many cases, as result aggregation active species to Pd black possible side during each bond-forming step. The two current solutions addressing these issues are either utilize...

A gold nanocluster Au17 Cd2 (PNP)2 (SR)12 (PNP=2,6-bis(diphenylphosphinomethyl)pyridine, SR=4-MeOPhS) consisting of an icosahedral Au13 kernel, two Au2 CdS6 staple motifs, and PNP pincer ligands has been designed, synthesized well characterized. This cadmium ligand co-modified showed high catalytic efficiency in the KA2 reaction, featuring TON, mild reaction conditions, broad substrate scope as catalyst recyclability. Comparison performance between structurally similar single (or PNP)...

Electrochemical synthesis of ammonia from stable dinitrogen molecules has attracted substantial research interest recently.

The direct coupling of aldehydes with petrochemical feedstock alkenes and alkynes would represent a practical streamlined approach for allylation allenylation chemistry. However, conventional approaches commonly require preactivated substrates or strong bases to generate allylic propargylic carbanions only afford branched propargylation products. Developing mild selective access synthetically useful linear products is highly desirable, albeit formidable challenges. We report strategy using...

Practical approaches to the synthesis of atomically precise metal nanoclusters are in high demand as they provide structural basis for investigating nanomaterials' structure-property correlations with atomic precision. The Brust-Schiffrin method has been widely used, while essential reductive ligands (e.g., thiols) limit application this synthesizing specific frameworks and surface ligands. In work, we developed a photochemical route by applying disulfide, which is available, stable,...

Abstract Selective functionalization of allenic C(sp 2 )‐H is an ideal approach to upgrading simple allenes synthetically useful allenes, albeit suffering from challenges associated with inert reactivity and inferior selectivity. Inspired by energy chemistry, a catalytic hydrogen evolution reaction (HER) strategy was leveraged selectively activate weakly acidic allene bonds in reductive mode. An array [Co O ] metallacycle complexes were readily devised starting amino acids, they demonstrated...

The first highly efficient double Friedel–Crafts reaction of N-tosyl imines with anisole, phenol, thioanisole and analogues has been developed to produce the corresponding symmetric diarylmethanes triarylmethanes high regioselectivity in presence a catalytic amount Bi2(SO4)3–TMSCl at room temperature.