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A new dicationic cluster, [Cu21S2{S2CNnBu2}9(C2Ph)6]2+, where the Cu21S2 kernel consists of two S@Cu12 cuboctahedra sharing a triangular Cu3 face is reported. Its waist part is bridged by three dithiocarbamate ligands, each in a hexaconnective, hexametallic (μ3, μ3) coordination pattern, an unprecedented feature in Cu nanocluster chemistry. [ABSTRACT FROM AUTHOR]

Modification of μ 4 -H trigonal pyramidal (tp) geometry in PtH 2 Cu 14 -dtp into μ 5 -H trigonal bipyramidal (tbp) in PtH 2 Cu 14 -dtc can be achieved through the replacement of supporting dithiophosphate (dtp) with dithiocarbamate (dtc) ligands. [Display omitted] An atomically precise heteroleptic Pt-doped Cu-rich hydride nanocluster [PtH 2 @Cu 14 (dtc) 6 (C 2 Ph) 6 ] (PtH 2 Cu 14 -dtc) has been successfully synthesized. This was achieved by introducing a discrete Pt(II) precursor to the copper hydride nanocluster [Cu 28 H 15 (dtc) 12 ](PF 6) in the presence of terminal alkynes. The structure of PtH 2 Cu 14 determined by X-ray diffraction reveals a bicapped icosahedral copper(I) cage encapsulating a linear platinum dihydride [PtH 2 ]2- unit. The interstitial hydrides are arranged in a trigonal bipyramidal (tbp) geometry with a five-coordinated hydride as confirmed by 2H NMR and ESI-MS measurements. [ABSTRACT FROM AUTHOR]

The bimetallic M20 and M21 compounds, {[Cu3Ag17{S2P(OiPr)2}12]0.5 [Cu4Ag16{S2P(OiPr)2}12]0.5} ({[1a]0.5[1b]0.5}) and [Cu4Ag17{S2P(OiPr)2}12](PF6) (2), have been structurally characterized, in which the Cu(I) ions are randomly distributed on the eight outer positions capping the eight-electron [Ag13]5+ core. DFT calculations show that the statistical disorder results from the nearly neutral preference of copper to occupy any of the eight outer positions. Surprisingly, the UV–Vis absorption spectra of the M20 and M21 bimetallic nanoclusters display an almost identical absorption profile as that of their homometallic [Ag20{S2P(OiPr)2}12] and [Ag21{S2P(OiPr)2}12]+ relatives. This is rationalized by TD-DFT calculations, which show that the frontier orbitals of such eight-electron alloys are largely independent from the nature of the capping metal ions. A blue-shifted absorption is observed upon replacing by Au the central Ag atom in 2, forming the trimetallic compound [Cu4AuAg16{S2P(OiPr)2}12](PF6) (3). [ABSTRACT FROM AUTHOR]

The first 8‐electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg19(dtp)12] (dtp=S2P(OiPr)2−) 1 and [PdHAg20(dtp)12]+2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55 % yield. Further modification of the shell results in the formation of [PdAg21(dtp)12]+3 via an internal redox reaction, with the system retaining an 8‐electron superatomic configuration. The interstitial hydride in 1 and 2 contributes its 1s1 electron to the superatomic electron count and occupies a PdAg3 tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT NMR spectroscopy. The emissive state of 3 has a lifetime of 200 μs (λex=448; λem=842), while 1 and 2 are non‐emissive. The catalytic reduction of 4‐nitrophenol is demonstrated with 1–3 at room temperature. [ABSTRACT FROM AUTHOR]

Atomically precise thiolate-protected coinage metal nanoclusters and their alloys are far more numerous than their selenium congeners, the synthesis of which remains extremely challenging. Herein, we report the synthesis of a series of atomically defined dithiophosph(in)ate protected eight-electron superatomic palladium silver nanoalloys [PdAg20{S2PR2}12], 2a–c (where R = OiPr, a; OiBu, b; Ph, c) via ligand exchange and/or co-reduction methods. The ligand exchange reaction on [PdAg20{S2P(OnPr)2}12], 1, with [NH4{Se2PR2}12] (where R = OiPr, or OnPr) leads to the formation of [PdAg20{Se2P(OiPr)2}12] (3) and [PdAg20{Se2P(OnPr)2}12] (4), respectively. Solid state structures of 2a, 2b, 3 and 4 unravel different PdAg20 metal frameworks from their parent cluster, originating from the different distributions of the eight-capping silver(I) atoms around a Pd@Ag12 centered icosahedron with C2,D3,Th and Th symmetries, respectively. Surprisingly ambient temperature crystallization of the reaction product 3 obtained by the ligand exchange reaction on 1 has resulted in the co-crystallization of two isomers in the unit cell with overall T (3a) and C3 (3b) symmetries, respectively. To our knowledge, this is the first ever characterized isomeric pair among the selenolate-protected NCs. Density functional theory (DFT) studies further rationalize the preferred geometrical isomerism of the PdAg20 core. Atomically and structurally precise silver nanoclusters hold great potential for catalytic and optoelectronic applications. Here, the authors synthesize and characterize a series of atomically defined dithio- and diselenophosphate-protected eight-electron superatomic palladium-doped silver nanoclusters, including an unprecedented pair of selenolate-protected isomers. [ABSTRACT FROM AUTHOR]

Rational syntheses under controllable reducing conditions in the preparation of superatoms with cluster electron number not exceeding two are challenging. Herein a dithiolate‐stabilized two‐electron silver nanocluster, Ag10{S2P(OiPr)2}8 (1), is isolated via a self‐redox reaction of Ag7(H){S2P(OiPr)2}6 without adding extra reducing agents. The metal framework of Ag7, a bicapped trigonal bipyramid, is highly correlated to that of Ag10, suggesting Ag7(H){S2P(OiPr)2}6 acts as both reducing agent and template in cluster growth. 1 is highly fluorescent at ambient temperature and TD‐DFT calculations indicate that the emission is of 1Px→1S nature. [ABSTRACT FROM AUTHOR]

Rational syntheses under controllable reducing conditions in the preparation of superatoms with cluster electron number not exceeding two are challenging. Herein a dithiolate‐stabilized two‐electron silver nanocluster, Ag10{S2P(OiPr)2}8 (1), is isolated via a self‐redox reaction of Ag7(H){S2P(OiPr)2}6 without adding extra reducing agents. The metal framework of Ag7, a bicapped trigonal bipyramid, is highly correlated to that of Ag10, suggesting Ag7(H){S2P(OiPr)2}6 acts as both reducing agent and template in cluster growth. 1 is highly fluorescent at ambient temperature and TD‐DFT calculations indicate that the emission is of 1Px→1S nature. [ABSTRACT FROM AUTHOR]

A structurally precise hydride‐containing Pt‐doped Cu‐rich nanocluster [PtH2Cu14{S2P(OiPr)2}6(CCPh)6] (1) has been synthesized. It consists of a bicapped icosahedral Cu14 cage that encapsulates a linear PtH2 unit. Upon the addition of two equivalents of CF3COOH to 1, two hydrido clusters are isolated. These clusters are [PtHCu11{S2P(OiPr)2}6(CCPh)4] (2), which is a vertex‐missing Cu11 cuboctahedron encaging a PtH moiety, and [PtH2Cu11{S2P(OiPr)2}6(CCPh)3] (3), a distorted 3,3,4,4,4‐pentacapped trigonal prismatic Cu11 cage enclosing a PtH2 unit. The electronic structure of 2, analyzed by Density Functional Theory, is a 2e superatom. The electrocatalytic activities of 1–3 for hydrogen evolution reaction (HER) were compared. Notably, Cluster 2 exhibited an exceptionally excellent HER activity within metal nanoclusters, with an onset potential of −0.03 V (at 10 mA cm−2), a Tafel slope of 39 mV dec−1, and consistent HER activity throughout 3000 cycles in 0.5 M H2SO4. Our study suggests that the accessible central Pt site plays a crucial role in the remarkable HER activity and may provide valuable insights for establishing correlations between catalyst structure and HER activity. [ABSTRACT FROM AUTHOR]

Encouraged by the successful syntheses of alloy nanoclusters (or nanoparticles) via intercluster (or interparticle) reactions, herein we apply this methodology to prepare a series of bimetallic hydride clusters. Mixing of two clusters, [Ag7(H){E2P(OiPr)2}6] (E = S, 1; Se, 3) and [Cu7(H){E2P(OiPr)2}6] (E = S, 2; Se, 4), yields two series of hydride-centered bimetallic clusters, [CuxAg7−x(H){E2P(OiPr)2}6] (x = 0–7; E = S, 5; Se, 6). Their compositions are fully characterized by positive-mode ESI-MS spectrometry, multi-NMR spectroscopy, and the structures of [Cu6Ag(H){S2P(OiPr)2}6] (5a) and [CuAg6(H){Se2P(OiPr)2}6] (6a) by single crystal X-ray diffraction. The presence of individual compounds in solution is the result of a (dynamic) chemical equilibrium primarily driven by metal exchanges. In fact, the process of inter-cluster exchange of 1 and 2 leading to hydride-centered bimetallic clusters 5 can be monitored by concentration-dependent 31P NMR spectroscopy of which the higher concentration of 1 in the reaction, the closer to its resonance will be the distribution, in accord with Le Chatelier's principle. The dynamic equilibrium is further confirmed by 2D exchange spectroscopy that reveals a stepwise process involving one metal exchange at a time. DFT calculations on a model series of clusters 6 show that silver prefers occupying the inner tetrahedral positions, while copper favors capping positions, in full agreement with the crystal structure of 5a and 6a. [ABSTRACT FROM AUTHOR]

Two mixed-metal hydride clusters, corresponding to x = 3 and 4, were structurally characterized from a set of atomically precise heptanuclear clusters, CuxAg7−x(H){S2P(OiPr)2}6 (x = 1–6). An interstitial hydride lying at the center of a tricapped tetrahedral cage was located and refined anisotropically by using X-ray data, and its presence acertained by multinuclear NMR spectroscopy and DFT calculations. [ABSTRACT FROM AUTHOR]

We herein reported a concise synthesis of a new class of tetrazolyl‐benzothiazoles (TBTs). This synthesis was achieved via a microwave‐assisted ANRORC method followed by an acid‐catalyzed [2 + 3] cycloaddition. The TBT core was elaborated with diverse substituents at the N‐1 or N‐2 position on the tetrazole ring to create a compound library for further bioactivity evaluation. The newly synthesized TBT‐based compounds were assessed for their inhibitory effects against human breast cancer cell lines, MCF‐7 and MDA‐MB‐231. Our results revealed that N‐2 substituted TBTs were generally more active than their N‐1 isomers, and 11g emerged as the most potent inhibitor with IC50 values of 5.3 and 10.4 μg/mL against MCF‐7 and MDA‐MB‐231, respectively. This study provides new insights into the synthesis and anticancer inhibitory activity of TBTs, highlighting their potential for future drug development. [ABSTRACT FROM AUTHOR]

The structurally precise Cu‐rich hydride nanoclusters [PdCu14H2(dtc/dtp)6(C≡CPh)6] (dtc: di‐butyldithiocarbamate (1); dtp: di‐isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu28H15(S2CNnBu2)12]+ or [Cu20H11{S2P(OiPr)2}9] with phenyl acetylene in the presence of Pd(PPh3)2Cl2. Their structures and compositions were determined by single‐crystal X‐ray diffraction and the results supported by ESI‐mass spectrometry. Hydride positions in 1 were confirmed by single‐crystal neutron diffraction. Each hydride is connected to one Pd0 and four CuI atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH2]2− unit and its Cu14 bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded. Come in number 14: A unique methodology was used to synthesize atomically precise palladium‐alloyed copper hydride clusters. X‐ray and neutron diffraction revealed that a 14‐electron [PdH2]2− unit is iono‐covalently encapsulated within a bicapped icosahedral [Cu14]14+ cage and, as a result, the central Pd0 adopts the coordination number of 14. [ABSTRACT FROM AUTHOR]

The first hydride‐containing 2‐electron palladium/copper alloys, [PdHCu11{S2P(OiPr)2}6(C≡CPh)4] (PdHCu11) and [PdHCu12{S2P(OiPr)2}5{S2PO(OiPr)} (C≡CPh)4] (PdHCu12), are synthesized from the reaction of [PdH2Cu14{S2P(OiPr)2}6(C≡CPh)6] (PdH2Cu14) with trifluoroacetic acid (TFA). X‐ray diffraction reveals that the PdHCu11 and PdHCu12 kernels consist of a central PdH unit encapsulated within a vertex‐missing Cu11 cuboctahedron and complete Cu12 cuboctahedron, respectively. DFT calculations indicate that both PdHCu11 and PdHCu12 can be considered as axially‐distorted 2‐electron superatoms. PdHCu11 shows excellent HER activity, unprecedented within metal nanoclusters, with an onset potential of −0.05 V (at 10 mA cm−2), a Tafel slope of 40 mV dec−1, and consistent HER activity during 1000 cycles in 0.5 M H2SO4. Our study suggests that the accessible central Pd site is the key to HER activity and may provide guidelines for correlating catalyst structures and HER activity. [ABSTRACT FROM AUTHOR]

The first hydride‐containing 2‐electron palladium/copper alloys, [PdHCu11{S2P(OiPr)2}6(C≡CPh)4] (PdHCu11) and [PdHCu12{S2P(OiPr)2}5{S2PO(OiPr)} (C≡CPh)4] (PdHCu12), are synthesized from the reaction of [PdH2Cu14{S2P(OiPr)2}6(C≡CPh)6] (PdH2Cu14) with trifluoroacetic acid (TFA). X‐ray diffraction reveals that the PdHCu11 and PdHCu12 kernels consist of a central PdH unit encapsulated within a vertex‐missing Cu11 cuboctahedron and complete Cu12 cuboctahedron, respectively. DFT calculations indicate that both PdHCu11 and PdHCu12 can be considered as axially‐distorted 2‐electron superatoms. PdHCu11 shows excellent HER activity, unprecedented within metal nanoclusters, with an onset potential of −0.05 V (at 10 mA cm−2), a Tafel slope of 40 mV dec−1, and consistent HER activity during 1000 cycles in 0.5 M H2SO4. Our study suggests that the accessible central Pd site is the key to HER activity and may provide guidelines for correlating catalyst structures and HER activity. [ABSTRACT FROM AUTHOR]

A neutral polyhydrido copper cluster, [Cu27H15{S2CNnBu2}12] (abbreviated as [Cu27H15]), was prepared by the reaction of dithiocarbamates (dtc), Cu(I) salts and NaBH4. The isolated cluster provides insights into core engineering, demonstrating its novel ability to reversibly add or remove one copper atom from the cluster core. Single-crystal X-ray analysis reveals that the new core–shell structure exhibits a Cu24 rhombicuboctahedral outer cage and an inner Cu3 triangular kernel. The two core–shell clusters, [Cu27H15{S2CNnBu2}12] and previously published [Cu28H15(S2CNnBu2)12]+ (abbreviated as [Cu28H15]+), are only differentiated by one copper atom in their inner core. Importantly, we demonstrate core engineering with the controllable reversible transition between an irregular Cu4 tetrahedron and a Cu3 triangle, whilst maintaining their outer Cu24 shell intact. The 15 hydride atoms in [Cu27H15], coordinated in three different modes, are co-incident with the hydride positions in [Cu28H15]+. The degradation of [Cu27H15] in solution or the addition of one eq. of Cu(I) ions leads to the conversion of [Cu27H15] into [Cu28H15]+, while the reverse transformation can be achieved by the addition of either formic acid or a reducing agent to [Cu28H15]+. A dicationic species was observed in the ESI mass spectrum, and the composition is formulated as [Cu56H30(S2CNnBu2)24]2+, a dimer of [Cu27H15(S2CNnBu2)12 + Cu+]22+. The dimeric species was further explored by DFT calculations, suggesting that the lowest energy structure consists of a [Cu28H15]+ and a [Cu27H15] cluster connected through one Cu+ atom bridge. As a result, [Cu27H15] is considered an intermediate species in the formation of the more stable [Cu28H15]+ nanoball. [ABSTRACT FROM AUTHOR]

Two series of hyper-coordinated halide-centered M12 cuboctahedral clusters, [M12(μ12-X){S2P(OnPr)2}6{C≡CPh}4](PF6), 1a–c and 2a–c (where M = Cu, 1; Ag, 2; X = Cl, a; Br, b; I, c), were synthesized and fully characterized by ESI-MS, multi-NMR spectroscopy, IR and UV-Vis spectroscopy, photoluminescence analysis, and single-crystal X-ray crystallography. Structures 1c, 2b, and 2c show a twelve-coordinated halide encapsulated in the M12 cage, which is stabilized by six dithiophosphate and four alkynyl ligands. Compound 2b is the first Ag(I) cluster containing a twelve-coordinated bromide. The structural features of all six clusters are highly similar, providing a comparison basis of the inverse coordination for halides. Besides, the detailed structural analysis illustrates how the inverse coordination of a halide has influenced the size of the cuboctahedral M12 framework. [ABSTRACT FROM AUTHOR]

The benzyl‐ and amido‐substituted benzimidazolium ligand precursor [Bz‐BimH‐CH2CONH2]Br (1) was synthesized. Under different conditions, the reactions of this ligand precursor with PdBr2 produced palladium carbene complexes: Pd[(Bz‐Bim‐CH2CONH2)2Br2] (2), Pd(Bz‐Bim‐CH2CONH)2 (3), [Pd(Bz‐Bim‐CH2CONH2)(Py)Br2] (4), or [Pd(Bz‐Bim‐CH2CONH2)(CH3CN)Br2] (5). These complexes were characterized by NMR, IR, and single‐crystal X‐ray diffraction analyses. Complex 2 contains two trans rotamers in both the solution and solid state, and a crystal that possesses a trans‐anti conformation is confirmed through single‐crystal X‐ray diffraction analysis. Complex 3 contains two cis‐orientated bidentate carbene ligands, and complexes 4 and 5 are mono‐carbene complexes. The chelate rings in complex 3 rendered the methylene protons of the amido‐substituted diastereotopic, and a long range (six bond) through bond interaction between the carbonyl carbon and the methylene protons of the benzyl‐substituent was observed through the HMBC experiment. The catalytic activity studies indicated 4 and 5 are better catalysts in Suzuki‐Miyaura coupling reaction. [ABSTRACT FROM AUTHOR]

The introduction of CF 3 COOH to PdH 2 Cu 14 leads to modifications in the metallic core structure of the nanocluster. The controlled degradation of PdH 2 Cu 14 is facilitated by the acidic environment, resulting in the formation of many clusters with different metal core geometries and optical properties, including the 2e superatoms PdHCu 11 , PdHCu 12 , and the new PdH 2 Cu 11 cluster. [Display omitted] • A quasi-linear H-Pd-H unit embedded in a distorted 3,3,4,4,4-pentacapped trigonal prism Cu 11 has been characterized. • Symmetry-independent of PdH 2 Cu 11 presented unique inter-cluster π···π interaction in hexagonal packing arrangement. • The unsymmetrical coordination modes of the two H atoms were identified by SC-XRD. • Different types of PhC C- coordination mode on three symmetry-independent molecules. • The inclusion complex between [PdH 2 ]2− and Cu 11 cage was indicated by computational studies. • Its structure, hydride position, and optical properties are optimized and rationalized through DFT and TD-DFT calculations. A crucial component of nanocluster (NC) chemistry is the design and control of complex molecular architectures with atomic precision. Herein, we report the synthesis and structure of [PdH 2 Cu 11 {S 2 P(O i Pr) 2 } 6 (C CPh) 3 ] (PdH 2 Cu 11), confirmed by single-crystal X-ray diffraction (SC-XRD), NMR spectroscopy, elemental analysis, and electrospray ionization mass spectrometry (ESI-MS). PdH 2 Cu 11 is obtained from the reaction of a parent cluster [PdH 2 Cu 14 {S 2 P(O i Pr) 2 } 6 (C CPh) 6 ] (PdH 2 Cu 14) with trifluoroacetic acid (TFA). Importantly the addition of TFA does not result in the loss of the hydride atoms located at the kernel, and H-Pd-H motif is retained. The molecular structure of PdH 2 Cu 11 consists of a distorted 3,3,4,4,4-pentacapped trigonal prism Cu 11 cage encapsulating a quasi-linear H-Pd-H unit, stabilized by dithiophosphate and alkynyl ligands. DFT calculations suggest an ionic inclusion complex of the type [{PdH 2 }2−]@[{Cu 11 {S 2 P(O i Pr) 2 } 6 (C CPh) 3 }2+] and confirm the hydride positions. A non-covalent inter-cluster interaction results in the unique formation of a unique honeycomb crystal lattice. Overall, this work broadens and deepens the understanding of Pd-Cu hydride alloy nanoclusters. [ABSTRACT FROM AUTHOR]

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu+, Ag+, and Au+), the stable CuI dihydride template [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] (H2Cu11) generates surprisingly three very different compounds, namely [CuH2Cu11{S2P(OiPr)2}6(C≡CPh)3]+ (1), [AgH2Cu14{S2P(OiPr)2}6((C≡CPh)6]+ (2), and [AuCu11{S2P(OiPr)2}6(C≡CPh)3Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H2Cu11 precursor. Neutron diffraction revealed the first time a trigonal‐pyramidal hydride coordination mode in the AgCu3 environment of 2. 3 has no hydride and exhibits a mixed‐valent [AuCu11]10+ metal core, making it a two‐electron superatom. [ABSTRACT FROM AUTHOR]

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu+, Ag+, and Au+), the stable CuI dihydride template [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] (H2Cu11) generates surprisingly three very different compounds, namely [CuH2Cu11{S2P(OiPr)2}6(C≡CPh)3]+ (1), [AgH2Cu14{S2P(OiPr)2}6((C≡CPh)6]+ (2), and [AuCu11{S2P(OiPr)2}6(C≡CPh)3Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H2Cu11 precursor. Neutron diffraction revealed the first time a trigonal‐pyramidal hydride coordination mode in the AgCu3 environment of 2. 3 has no hydride and exhibits a mixed‐valent [AuCu11]10+ metal core, making it a two‐electron superatom. [ABSTRACT FROM AUTHOR]

A decanuclear silver chalcogenide cluster, [Ag10(Se){Se2P(OiPr)2}8] (2) was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag7(H){Se2P(OiPr)2}6], under thermal condition. The time-dependent NMR spectroscopy showed that 2 was generated at the first three hours and the hydrido silver cluster was completely consumed after thirty-six hours. This method illustrated as cluster-to-cluster transformations can be applied to prepare selenide-centered decanuclear bimetallic clusters, [CuxAg10-x(Se){Se2P(OiPr)2}8] (x = 0–7, 3), via heating [CuxAg7−x(H){Se2P(OiPr)2}6] (x = 1–6) at 60 °C. Compositions of 3 were accurately confirmed by the ESI mass spectrometry. While the crystal 2 revealed two un-identical [Ag10(Se){Se2P(OiPr)2}8] structures in the asymmetric unit, a co-crystal of [Cu3Ag7(Se){Se2P(OiPr)2}8]0.6[Cu4Ag6(Se){Se2P(OiPr)2}8]0.4 ([3a]0.6[3b]0.4) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of 2, [3a]0.6[3b]0.4 and the previous published [Ag10(Se){Se2P(OEt)2}8] (1) are quite similar (10 metals, 1 Se2−, 8 ligands), their metal core arrangements are completely different. These results show that different synthetic methods by using different starting reagents can affect the structure of the resulting products, leading to polymorphism. [ABSTRACT FROM AUTHOR]

Inside Back Cover: A Two-Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride (Angew. Hydrides, redox reactions, silver, silver nanoclusters, superatoms Keywords: hydrides; redox reactions; silver; silver nanoclusters; superatoms EN hydrides redox reactions silver silver nanoclusters superatoms 13113 13113 1 05/28/21 20210601 NES 210601 B A new methodology b was developed for the preparation of superatomic nanoclusters in a controllable fashion, with an internal redox reaction of Ag SB 7 sb (H)L SB 6 sb leading to the formation of a highly emissive two-electron Ag nanocluster, Ag SB 10 sb L SB 8 sb . [Extracted from the article]

Hydrides, redox reactions, silver, silver nanoclusters, superatoms Keywords: hydrides; redox reactions; silver; silver nanoclusters; superatoms EN hydrides redox reactions silver silver nanoclusters superatoms 13223 13223 1 05/28/21 20210601 NES 210601 B Eine neue Methode b zur kontrollierbaren Herstellung von superatomaren Nanoclustern wurde entwickelt, bei der eine interne Redoxreaktion von Ag SB 7 sb (H)L SB 6 sb zur Bildung eines hochemittierenden Ag-Nanoclusters Ag SB 10 sb L SB 8 sb führt. Innenrücktitelbild: A Two-Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride (Angew. [Extracted from the article]

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate‐protected copper(I) hydride‐rich nanocluster (NC), [Cu30H18{S2P(OnPr)2}12] (1H), fully characterized by various spectroscopic methods and single‐crystal X‐ray diffraction. The X‐ray structure of 1H reveals an unprecedented central Cu12 hollow icosahedron. Six faces of this icosahedron are capped by Cu3 triangles, the whole Cu30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S6 symmetry. The locations of the 18 hydrides in 1H were ascertained by a single‐crystal neutron diffraction study. They are composed of three types: capping μ3‐H, interstitial μ4‐H (seesaw) and μ5‐H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1H NMR spectrum of 1H are in line with their coordination environment in the solid state, retaining the S6 symmetry in solution. Furthermore, two new Se‐protected polyhydrido copper nanoclusters, [Cu30H18{Se2P(OR)2}12] (2H: R=iPr 3H: R=iBu) were synthesized from their sulfur relative 1H via ligand displacement reaction and their X‐ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD‐DFT calculations allow understanding the bonding and optical properties of clusters 1H–3H. In addition, the reaction of 1H with [Pd(PPh3)2Cl2] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu14H2{S2P(OnPr)2}6(C≡CR)6] (4: R=Ph; 5: R=C6H4F). [ABSTRACT FROM AUTHOR]

Keywords: NHC carbenes; palladium; catalytic reaction; C-C coupling EN NHC carbenes palladium catalytic reaction C-C coupling 1 1 1 08/16/22 20220805 NES 220805 GRAPH Conflict of interest The authors declare no conflict of interest. NHC carbenes, palladium, catalytic reaction, C-C coupling Corrigendum: Synthesis and Structures of Benzyl- and Amido-Substituted N-Heterocyclic Palladium Carbene Complexes. [Extracted from the article]

Keywords: cluster compounds; copper; gold; neutron diffraction; silver EN cluster compounds copper gold neutron diffraction silver 1 1 1 01/06/22 20220110 NES 220110 B Depending on the nature of M SP + sp b , the hydrides of the H SB 2 sb Cu SB 11 sb reactant behave differently. Cluster compounds, copper, gold, neutron diffraction, silver In the case of M=Cu or Ag, they act as regular two-electron ligands yielding [CuH SB 2 sb Cu SB 11 sb {S SB 2 sb P(O SP I i i sp Pr) SB 2 sb } SB 6 sb (C CPh) SB 3 sb ] SP + sp (Cu SB 12 sb H SB 2 sb ) or [AgH SB 2 sb Cu SB 14 sb {S SB 2 sb P(O SP I i i sp Pr) SB 2 sb } SB 6 sb (C CPh) SB 6 sb ] SP + sp (AgH SB 2 sb Cu SB 14 sb ); in the case of M=Au, they behave as electron donors to form [AuCu SB 11 sb {S SB 2 sb P(O SP I i i sp Pr) SB 2 sb } SB 6 sb (C CPh) SB 3 sb Cl] (AuCu SB 11 sb ). [Extracted from the article]

Keywords: cluster compounds; copper; gold; neutron diffraction; silver EN cluster compounds copper gold neutron diffraction silver 1 1 1 01/10/22 20220110 NES 220110 B Je nach M SP + sp b verhalten sich die Hydride des H SB 2 sb Cu SB 11 sb -Reaktanten unterschiedlich. Cluster compounds, copper, gold, neutron diffraction, silver Innentitelbild: Reactivities of Interstitial Hydrides in a Cu11 Template: En Route to Bimetallic Clusters (Angew. [Extracted from the article]