Paired electrocatalysis unlocks cross-dehydrogenative coupling of C(sp3)-H bonds using a pentacoordinated cobalt-salen catalyst.

Cross-dehydrogenative coupling of C(sp3)-H bonds is an ideal approach for C(sp3)-C(sp3) bond construction. However, conventional approaches mainly rely on a single activation mode by either stoichiometric oxidants or electrochemical oxidation, which would lead to inferior selectivity in the reaction between similar C(sp3)-H bonds. Herein we describe our development of a paired electrocatalysis strategy to access an unconventional selectivity in the cross-dehydrogenative coupling of alcoholic α C(sp3)-H with allylic (or benzylic) C-H bonds, which combines hydrogen evolution reaction catalysis with hydride transfer catalysis. To maximize the synergistic effect of the catalyst combinations, a HER catalyst pentacoordinated Co-salen is disclosed. The catalyst displays a large redox-potential gap (1.98 V) and suitable redox potential. With the optimized catalyst combination, an electrochemical cross-dehydrogenative coupling protocol features unconventional chemoselectivity (C-C vs. C-O coupling), excellent functional group tolerance (84 examples), valuable byproduct (hydrogen), and high regio- and site-selectivity. A plausible reaction mechanism is also proposed to rationalize the experimental observations.

Site-Recognition-Induced Structural and Photoluminescent Evolution of the Gold-Pincer Nanocluster.

The induced structural transformation provides an efficient way to precisely modulate the fine structures and the corresponding performance of gold nanoclusters, thus constituting one of the important research topics in cluster chemistry. However, the driving forces and mechanisms of these processes are still ambiguous in many cases, limiting further applications. In this work, based on the unique coordination mode of the pincer ligand-stabilized gold nanocluster Au8(PNP)4, we revealed the site-recognition mechanism for induced transformations of gold nanoclusters. The "open nitrogen sites" on the surface of the nanocluster interact with different inducers including organic compounds and metals and trigger the conversion of Au8(PNP)4 to Au13 and Au9Ag4 nanoclusters, respectively. Control experiments verified the site-recognition mechanism, and the femtosecond and nanosecond transient absorption spectroscopy revealed the electronic and photoluminescent evolution accompanied by the structural transformation.

A Hydrogen Evolution Catalyst [Co2O2] Metallacycle Enables Regioselective Allene C(sp2)-H Functionalization.

Selective functionalization of allenic C(sp2)-H is an ideal approach to upgrading simple allenes to 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 to selectively activate weakly acidic allene C(sp2)-H bonds in a reductive mode. An array of [Co2O2] metallacycle complexes were readily devised starting from amino acids, and they were demonstrated as robust HER catalysts, which would selectively break allenic C(sp2)-H bonds to release hydrogen. With the newly developed HER catalyst, regioselective electrochemical functionalization of allenic C(sp2)-H with alcoholic α C(sp3)-H was unprecedentedly achieved. This strategy features excellent regioselectivity, unconventional chemoselectivity, good functional-group tolerance (62 examples), and mild conditions. Mechanism experiments revealed a reactive hydroxy-coordinated cobalt(II) species in the reaction. Density functional theory (DFT) calculations were also conducted to rationalize the regioselectivity observed in the reaction.

Building Block Metal Nanocluster-Based Growth in 1D Direction.

Metal nanoclusters with precisely modulated structures at the nanoscale give us the opportunity to synthesize and investigate 1D nanomaterials at the atomic level. Herein, it realizes selective 1D growth of building block nanocluster "Au13 Cd2 " into three structurally different nanoclusters: "hand-in-hand" (Au13 Cd2 )2 O, "head-to-head" Au25 , and "shoulder-to-shoulder" Au33 . Detailed studies further reveals the growth mechanism and the growth-related tunable properties. This work provides new hints for the predictable structural transformation of nanoclusters and atomically precise construction of 1D nanomaterials.

Reduction-Oxidation Cascade Strategy for Reforming a Au13-Kerneled Gold Thiolate Nanocluster.

Gold nanoclusters protected by thiolate ligands are ideal models for investigating the structure-property correlation of nanomaterals. Introducing relatively weak coordinating ligands into gold thiolate nanoclusters and thus reforming their structures is beneficial for further releasing their activities. However, controlling the selectivity of the process is a challenging task. In this work, we report a cascade strategy for deeply and purposefully reforming the structures of gold thiolate nanoclusters, exemplified by a Au13-kerneled Au23 nanocluster. Specifically, weakly coordinated triphenylphosphine was utilized to reduce (activate) the surface of Au23, enabling its further structural reformation by the following oxidation step. A structurally distinctive Au20 nanocluster was obtained based on this reduction-oxidation cascade strategy. Mechanism studies reveal that both the reduction and oxidation steps and their working sequence are critical for the transformation. Theoretical and experimental results all indicate that the deep structural reformation results in the evolution of the electronic and photoluminescent properties of the gold thiolate nanocluster.

Photochemical synthesis of group 10 metal nanoclusters for electrocatalysis.

Four group 10 metal nanoclusters, Ni10(4-MePhS)20, Ni11(PhS)22, Pd9(PhS)18 and Pd10(PhS)20 were synthesized from disulfides based on a photochemical reduction-oxidation cascade process, which proceeds via a different mechanism to that of the conventional two-step reduction process. The as-obtained nanoclusters possess oxidative resistance and structural robustness under different conditions. Their atomically precise structures are determined to be nickel or palladium rings in which the metal atoms are bridged by Ar-S groups. Their catalytic performance in oxygen reduction reaction was compared, and the ring size-dependent catalytic activity of the group 10 metal nanoclusters was revealed. This work provides an efficient route to atomically precise and structurally stable group 10 metal nanoclusters, and sheds light on their further applications in electrocatalysis.

Photochemical Route for Synthesizing Atomically Precise Metal Nanoclusters from Disulfide.

Practical approaches to the synthesis of atomically precise metal nanoclusters are in high demand as they provide the structural basis for investigating nanomaterials' structure-property correlations with atomic precision. The Brust-Schiffrin method has been widely used, while the essential reductive ligands (e.g., thiols) limit the application of this method for synthesizing metal nanoclusters with specific frameworks and surface ligands. In this work, we developed a photochemical route for synthesizing atomically precise metal nanoclusters by applying disulfide, which is a widely available, stable, and environmentally friendly sulfur source. This method enables the construction of structurally diverse metal nanoclusters and especially features the synthesis of PhS-protected metal nanoclusters that were not easily achieved previously and the gram-scale synthesis. A reduction-oxidation cascade mechanism has been revealed for the photochemical route. This work is expected to open up new opportunities for metal nanocluster synthesis and will contribute to the practical applications of this kind of nanomaterial.

Electrochemically Generated Carbanions Enable Isomerizing Allylation and Allenylation of Aldehydes with Alkenes and Alkynes.

The direct coupling of aldehydes with petrochemical feedstock alkenes and alkynes would represent a practical and streamlined approach for allylation and allenylation chemistry. However, conventional approaches commonly require preactivated substrates or strong bases to generate allylic or propargylic carbanions and only afford branched allylation or propargylation products. Developing a mild and selective approach to access synthetically useful linear allylation and allenylation products is highly desirable, albeit with formidable challenges. We report a strategy using hydrogen evolution reaction (HER) to generate a carbanion from weakly acidic sp3 C-H bonds (pKa ∼ 35-40) under mild reaction conditions, obviating the use of strong bases, Schlenk techniques, and multistep procedures. The cathodically generated carbanion reverses the typical reaction selectivity to afford unconventional isomerizing allylation and allenylation products (125 examples). The generation of carbanions was monitored and identified by in situ ultraviolet-visible (UV-vis) spectroelectrochemistry. Furthermore, we extended this protocol to the generation of other carbanions and their application in coupling reactions between alcohols with carbanions. The appealing features of this approach include mild reaction conditions, excellent functional group tolerance, unconventional chemo- and regioselectivity, and the diverse utility of products, which includes offering direct access to diene luminophores and bioactive scaffolds. We also performed cyclic voltammetry, control experiments, and density functional theory (DFT) calculations to rationalize the observed reaction selectivity and mechanism.

Asymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excess.

The investigation of chirality at the nanoscale is important to bridge the 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 an efficient approach to enantiopure metal nanoclusters via asymmetric transformation, that is, achiral Au23(SC6H11)16 nanoclusters are converted into chiral and enantiopure Au24(L)2(SC6H11)16 nanoclusters by a chiral inducer phosphoramidite (L). Two enantiomers of Au24(L)2(SC6H11)16 are obtained and the crystal structures reveal their hierarchical chirality, which originates from the two introduced chiral L molecules, the transformation-triggered asymmetric rearrangement of the staple motifs on the surface of the gold core, and the helical arrangement of nanocluster molecules. The construction of this type of enantiomerically pure nanoclusters is achieved based on the easy-to-synthesize and modular L. Lastly, the chirality-related chiroptical performance was investigated, revealing a negative nonlinear CD-ee dependence.

Preorganized Nitrogen Sites for Au11 Amidation: A Generalizable Strategy toward Precision Functionalization of Metal Nanoclusters.

Atomically precise metal nanoclusters have received tremendous attention due to their unique structures and properties. Although synthetic approaches to this kind of nanomaterial have been well developed, methods toward precision functionalization of the as-synthesized metal nanoclusters are extremely limited, hindering their interfacial modification and related performance improvement. Herein, an amidation strategy has been developed for the precision functionalization of the Au11 nanocluster based on preorganized nitrogen sites. The nanocluster amidation did not change the number of gold atoms in the Au11 kernel and their bonding mode to the surface ligands but slightly modified the arrangement of gold atoms with the introduction of functionality and chirality, thus representing a relatively mild method for the modification of metal nanoclusters. The stability and oxidation barrier of the Au11 nanocluster are also improved accordingly. The method developed here would be a generalizable strategy for the precision functionalization of metal nanoclusters.

Nanoclusterzyme for Dual Colorimetric Sensings: A Case Study on [Au14 (Dppp)5 I4 ]2.

The enzymatic activity of atomically precise metal nanoclusters has recently been recognized; however, the number of nanoclusterzymes is very small. Besides, the applications of nanoclusterzyme wait to be explored. Herein, a novel nanoclusterzyme is synthesized and its structure is majorly resolved by single-crystal X-ray diffraction and mass spectrometry, which reveal that the nanocluster consists of an Au13 icosahedron capped by an exterior shell including four I, three Dppp (1,3-bis(diphenylphosphino) propane) ligands, and a rarely reported Dppp-Au-Dppp handle staple, which contributes a lot to the enzyme activity of [Au14 (Dppp)5 I4 ]2+ nanocluster. The as-obtained nanocluster can catalyze oxygen to O2 •- under visible light irradiation with a specific activity up to 0.182 U·mg-1 and lead to the blue color of 3,3',5,5'-tetramethylbenzidine (TMB) in both solution and solid states. With the addition of acetylcholinesterase (AChE), the blue color of (Au14  + TMB) solution system disappears due to the nanoclusterzyme activity inhibition, but the further addition of organophosphorus pesticides (OPs) into the above mixture can restore the nanoclusterzyme and recover the blue color. Based on the color turn-off and on, the various nanoclusterzyme-containing systems are used to colorimetrically sense AChE and OPs with the detection limits reaching 0.04 mU·mL-1 and 0.02 ng·mL-1 , respectively.

Open Nitrogen Site-Induced Kinetic Resolution and Catalysis of a Gold Nanocluster.

The emerging metal nanocluster provides a platform for the investigation of structural features, unique properties, and structure-property correlation of nanomaterials at the atomic level. Construction of open sites on the surface of the metal nanocluster is a long-pursued but challenging goal. Herein, we realized the construction of "open organic sites" in a metal nanocluster for the first time. Specifically, we introduce the PNP (2,6-bis(diphenylphosphinomethyl)pyridine) pincer ligand in the synthesis of the gold nanocluster, enabling the construction of a structurally precise Au8(PNP)4 nanocluster. The rigidity and the unique bonding mode of PNP lead to open nitrogen sites on the surface of the Au8(PNP)4 nanocluster, which have been utilized as multifunctional sites in this work for efficient kinetic resolution and catalysis. The gold pincer nanocluster and the open nitrogen site-induced performance will be enlightening for the construction of multifunctional metal nanoclusters.

Cadmium-Doped and Pincer Ligand-Modified Gold Nanocluster for Catalytic KA2 Reaction.

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 two PNP pincer ligands has been designed, synthesized and well characterized. This cadmium and PNP pincer ligand co-modified gold nanocluster showed high catalytic efficiency in the KA2 reaction, featuring high TON, mild reaction conditions, broad substrate scope as well as catalyst recyclability. Comparison of the catalytic performance between Au17 Cd2 (PNP)2 (SR)12 and the structurally similar single cadmium (or PNP) modified gold nanoclusters demonstrates that the co-existence of the cadmium and PNP on the surface is crucial for the high catalytic activity of the gold nanocluster. This work would be enlightening for developing efficient catalysts for cascade reactions and discovering the catalytic potential of metal nanoclusters in organic transformations.

Structure and assembly of a hexanuclear AuNi bimetallic nanocluster.

An Au4Ni2 nanocluster containing a square-planar [-PPh2-Au-S-Au-]2 ring and two nickel-pincer arms is reported here. Abundant intra- and inter-cluster noncovalent interactions promote the assembly of the nanocluster into a porous framework material. The assembly-dependent unique solubility and photoluminescence were also investigated.

Partial Phosphorization: A Strategy to Improve Some Performance(s) of Thiolated Metal Nanoclusters Without Notable Reduction of Stability.

Thiolates endow metal nanoclusters with stability while sometimes inhibit the catalytic activity due to the strong M-S interaction (M: metal atom). To improve the catalytic activity and keep the stability to some extent, one strategy is the partial phosphorization of thiolated metal nanoclusters. This is demonstrated by successful partial phosphorization of Au23 (SC6 H11 )16 and by revealing that the products Au22 (SC6 H11 )14 (PPh3 )2 and Au22 (SC6 H11 )12 (PPh3 )4 , with varied degree of phosphorization, both show excellent activity in the photocatalytic oxidation of thioanisole without notable reduction of stability. Furthermore, Au22 (SC6 H11 )12 (PPh3 )4 exhibits better photoluminescence performance than the mother nanocluster Au23 (SC6 H11 )16 , indicating that partial phosphorization can also improve some other performance(s) except for the catalytic performance. The intermediates Au22-x Cux (SC6 H11 )12 (PPh3 )4 (x=1, 2) in the transformation from Au23 (SC6 H11 )16 (Au22 (SC6 H11 )14 (PPh3 )2 ) to Au22 (SC6 H11 )12 (PPh3 )4 were captured and identified by mass spectrometry and single crystal X-ray diffraction, which throws light on the understanding of the non-alloyed anti-galvanic reaction.

Efficient Heterogeneous Palladium Catalysts in Oxidative Cascade Reactions.

Palladium-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 of high palladium efficiency and selectivity in Pd-catalyzed oxidative cascade reactions is still challenging in many cases, as a result of the aggregation of active palladium species to Pd black and the possible side reactions during each bond-forming step. The two current solutions for addressing these issues are either to utilize oxidant-stable ligands or to use electron transfer mediators (ETMs). The former solution, which includes the use of amines, pyridines, sulfoxides, and carbene derivatives, inhibits aggregation of Pd0 during the catalytic cycle, while the latter solution facilitates reoxidation of Pd0 to PdII to improve the activity and selectivity. Following our long-standing interest in Pd-catalyzed oxidations, very recently we developed heterogeneous catalysts to resolve the issues mentioned above in oxidative cascade reactions. The heterogeneous palladium catalysts (Pd-AmP-MCF or Pd-AmP-CNC) comprise palladium nanoclusters (1-2 nm) immobilized on amino-functionalized siliceous mesocellular foam (MCF) or on crystalline nanocellulose (CNC), exhibiting high activity, selectivity as well as excellent recycling ability.In this Account, we will discuss the synthesis and characterizations of the heterogeneous palladium catalysts, as well as their catalytic behaviors, and the mechanisms involved in their reactions. An important aspect of these catalysts in oxidation reactions is the generation of active Pd(II) species within the heterogeneous phase. Typical oxidative cascade reactions of our recent research on this topic include oxidative carbocyclization-carbonylation, oxidative carbocyclization-borylation, oxidative alkynylation-cyclization, oxidative carbonylation-cyclization, and oxidative carbocyclization-alkynylation. These reactions provide access to important compounds attractive in medicinal chemistry and functional materials, such as γ-lactone/γ-lactam-based poly rings, cyclobutenols, highly substituted furans, and oxaboroles. During these processes, the heterogeneous catalysts exhibited much higher turnover numbers (TONs) than their homogeneous counterparts (e.g., Pd(OAc)2) as well as unique selectivity that cannot be achieved by homogeneous palladium catalysts. The origin of the high efficiency and unique selectivity of the heterogeneous catalysts was also investigated. Asymmetric syntheses for the construction of optically pure compounds were realized based on the excellent selectivity in these heterogeneous processes. Kinetic studies revealed that the rate and yield of the reactions were essentially maintained during recycling, which demonstrates that Pd-AmP-MCF and Pd-AmP-CNC are robust and highly active in these oxidative cascade reactions. In addition, inductively coupled plasma optical emisson spectroscopy (ICP-OES) analysis and hot filtration test suggest that these processes most likely proceed via a heterogeneous pathway.Recent progress in our group has shown that the activity of Pd-AmP-MCF and Pd-AmP-CNC could be improved even further by the addition of Ag+ to generate cationic Pd(II). Furthermore, intriguing solvent effects were observed in a Pd-AmP-MCF-catalyzed oxidative cascade process, and solvent-controlled chemoselective transformations were developed based on this property of the catalyst. The heterogeneous strategy of this Account provides solutions to palladium deactivation and selectivity issues in Pd(II)-catalyzed oxidative cascade reactions and enables efficient catalyst recycling, which will open up new opportunities in oxidative cascade reactions.

Tailoring silver nanoclusters via doping: advances and opportunities.

Atomically precise noble metal nanoclusters (especially Au and Ag) have been pursued due to their fascinating molecule-like properties. In spite of the significant progress on Au nanoclusters (NCs), the structure and property evolution of Ag NCs is still in high demand. Doping is a useful strategy for improving the physicochemical performances of Ag NCs. Herein we summarize the recent advances in tailoring silver NC structures and properties via doping. First, we reviewed the recent studies on the synthesis of hetero metal atom doped silver bimetallic nanoclusters, which are classified by the dopants, including Au, Pt, Pd, Cu, Ni and Cd. Second, the doping effects on their properties were reviewed, including the locations of hetero metal atoms, the influence on their stability, and the charge state evolution. Moreover, we highlighted the doping-dependent improvement of the photo-luminescence (PL) performance and catalytic activity of Ag NCs.

Amino-Supported Palladium Catalyst for Chemo- and Stereoselective Domino Reactions.

A solid amino-supported palladium catalyst is used in an oxidative domino reaction for the diastereoselective construction of alkyne-substituted cyclopentenol compounds. This heterogeneous catalyst exhibits high efficiency and excellent chemoselectivity, as well as good recyclability. The chemoselectivity of the domino reactions was readily controlled by switching the solvent and catalyst. Asymmetric syntheses and an oxidative carbocyclization-borylation reaction have also been developed based on the heterogeneous palladium catalyst.

Silver-Triggered Activity of a Heterogeneous Palladium Catalyst in Oxidative Carbonylation Reactions.

A silver-triggered heterogeneous Pd-catalyzed oxidative carbonylation has been developed. This heterogeneous process exhibits high efficiency and good recyclability, and was utilized for the one-pot construction of polycyclic compounds with multiple chiral centers. AgOTf was used to remove chloride ions in the heterogeneous catalyst Pd-AmP-CNC, thereby generating highly active PdII , which results in high efficiency of the heterogeneous catalytic system.

Highly Diastereoselective Palladium-Catalyzed Oxidative Cascade Carbonylative Carbocyclization of Enallenols.

A palladium-catalyzed oxidative cascade carbonylative carbocyclization of enallenols was developed. Under mild reaction conditions, a range of cis-fused [5,5] bicyclic γ-lactones and γ-lactams with a 1,3-diene motif were obtained in good yields with high diastereoselectivity. The obtained lactone/lactam products are viable substrates for a stereoselective Diels-Alder reaction with N-phenylmaleimide, providing polycyclic compounds with increased molecular complexity.