Synthesis,Crystal Structure and Selected Properties of Mono(dithiocarbamato)‐gold(I), AuS2CNH2

The title compound AuS₂CNH₂ was prepared from an aqueous solution by reaction of dicyanidoaurate [Au(CN)₂]^– with excess of ammoniumdithiocarbamate NH₄S₂CN H ₂ at pH ≈ 2. The compound crystallizes in the orthorhombic space group Cmma with a = 6.4597(2), b = 12.6556(3), and c = 5.3235(1) Å. The crystal structure comprises linear S–Au–S dumbbells forming unbranched zigzag chains in combination with the dithiocarbamate ligands. The three‐dimensional arrangement of the molecules is realized by aurophilic Au^I–Au^I and hydrogen bonding interactions, respectively. AuS₂CNH₂ presents orange luminescence due to a broad emission band between 12000 cm^–1 and 23000 cm^–1 (ν = 26316 cm^–1).     

Oxygen Electroreduction Performance of Ultrasmall Gold Nanoclusters

Ultrasmall gold nanoclusters consisting of 2-4 Au atoms were synthesized and their performance in electrocatalytic oxygen reduction reactions (ORR) was examined. These clusters were synthesized by exposing AuPPh₃Cl to the aqueous ammonia medium for one week. Electrospray ionization mass spectrometry (ESI-MS), X-ray absorption fine structure (XAFS), and X-ray photoelectron spectroscopy (XPS) analyses indicate that the as-synthesized gold clusters (abbreviated as Au_x) consist of 2-4 Au atoms coordinated by the triphenylphosphine, hydroxyl, and adsorbed oxygen ligands. A glassy carbon disk electrode loaded with the Au_x clusters (Au_x/GC) was characterized by the cyclic and linear-sweep voltammetry for ORR. The cyclic voltammogram vs. RHE shows the onset potential of 0.87 V, and the kinetic parameters of J_K at 0.47 V and the electron-transfer number per oxygen molecule were calculated to be 14.28 mA/cm² and 3.96 via the Koutecky-Levich equations, respectively.     

Ring‐to‐Cage Structural Conversion via Template Effect in a Gold(I) Metallosupramolecular System

A unique example of a ring‐to‐cage structural conversion in a multinuclear gold(I) coordination system with d ‐penicillamine (d ‐H₂pen) is reported. The reaction of [Au₂Cl₂(dppe)] (dppe=1,2‐bis(diphenylphosphino)ethane) with d ‐H₂pen in a 1:1 ratio gave [Au₄(dppe)₂(d ‐pen)₂] ([ 1 ]), in which two [Au₂(dppe)]²⁺ units are linked by two d ‐pen S atoms in a cyclic form so as to have two bidentate‐N,O coordination arms. The subsequent reaction of [ 1 ] with Cu(OTf)₂ afforded [Au₄Cu(dppe)₂(d ‐pen)₂]²⁺ ([ 2 ]²⁺), in which a Cu^II ion is chelated by the two coordination arms in [ 1 ] to form an Au^I₄Cu^II bicyclic metallocage. A similar reaction using Cu(NO₃)₂ was accompanied by the ring expansion of [ 1 ] to [Au₈(dppe)₄(d ‐pen)₄], leading to the production of [Au₈Cu₂(dppe)₄(d ‐pen)₄]⁴⁺ ([ 3 ]⁴⁺). In [ 3 ]⁴⁺, two Cu^II ions are each chelated by the two coordination arms to form an Au^I₈Cu^II₂ tricyclic metallocage, accommodating a nitrate ion. The use of Ni(NO₃)₂ or Ni(OAc)₂ instead of Cu(NO₃)₂ commonly gave a tricyclic metallocage of [Au₈Ni₂(dppe)₄(d ‐pen)₄]⁴⁺ ([ 4 ]⁴⁺), but a water molecule was accommodated inside the Au^I₈Ni^II₂ metallocage.     

Luminescent Di‐ and Polynuclear Organometallic Gold(I)–Metal (Au2, {Au2Ag}n and {Au2Cu}n) Compounds Containing Bidentate Phosphanes as Active Antimicrobial Agents

The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au₂(mes)₂(μ‐LL)] (LL=dppe: 1,2‐bis(diphenylphosphano)ethane 1 a , and water‐soluble dppy: 1,2‐bis(di‐3‐pyridylphosphano)ethane 1 b ) with Ag⁺ and Cu⁺ lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au₂M(μ‐mes)₂(μ‐LL)][A] (M=Ag, A=ClO₄^?, LL=dppe 2 a , dppy 2 b ; M=Ag, A=SO₃CF₃^?, LL=dppe 3 a , dppy 3 b ; M=Cu, A=PF₆^?, LL=dppe 4 a , dppy 4 b ). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au₂(mes)₂(μ‐dppy)] ( 1 b ) and [Au₂Ag(μ‐mes)₂(μ‐dppe)][SO₃CF₃] ( 3 a ) were determined by a single‐crystal X‐ray diffraction study. 3 a in solid state is not a cyclic trinuclear Au₂Ag derivative but it gives an open polymeric structure instead, with the {Au₂(μ‐dppe)} fragments “linked” by {Ag(μ‐mes)₂} units. The very short distances of 2.7559(6) Å (Au? Ag) and 2.9229(8) Å (Au? Au) are indicative of gold–silver (metallophilic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self‐aggregation of [Au₂M(μ‐mes)₂(μ‐LL)]⁺ units (M=Ag or Cu; LL=dppe or dppy) into an extended chain structure, through Au? Au and/or Au? M metallophilic interactions, as that observed for 3 a . In solid state the heterometallic Au₂M complexes with dppe ( 2 a – 4 a ) show a shift of emission maxima (from ca. 430 to the range of 520‐540 nm) as compared to the parent dinuclear organometallic product 1 a while the complexes with dppy ( 2 b–4 b ) display a more moderate shift (505 for 1 b to a max of 563 nm for 4 b ). More importantly, compound [Au₂Ag(μ‐mes)₂(μ‐dppy)]ClO₄ ( 2 b ) resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au₂Cl₂(μ‐LL)] (LL dppy 5 b ) was also studied for comparative purposes. The antimicrobial activity of 1–5 and Ag[A] (A=ClO₄^?, SO₃CF₃^?) against Gram‐positive and Gram‐negative bacteria and yeast was evaluated. Most tested compounds displayed moderate to high antibacterial activity while heteronuclear Au₂M derivatives with dppe ( 2 a – 4 a ) were the more active (minimum inhibitory concentration 10 to 1 μg mL^?1). Compounds containing silver were ten times more active to Gram‐negative bacteria than the parent dinuclear compound 1 a or silver salts. Au₂Ag compounds with dppy ( 2 b , 3 b ) were also potent against fungi.     

Observation of Body‐Centered Cubic Gold Nanocluster

The structure of nanoparticles plays a critical role in dictating their material properties. Gold is well known to adopt face‐centered cubic (fcc) structure. Herein we report the first observation of a body‐centered cubic (bcc) gold nanocluster composed of 38 gold atoms protected by 20 adamantanethiolate ligands and two sulfido atoms ([Au₃₈S₂(SR)₂₀], where R=C₁₀H₁₅) as revealed by single‐crystal X‐ray crystallography. This bcc structure is in striking contrast with the fcc structure of bulk gold and conventional Au nanoparticles, as well as the bi‐icosahedral structure of [Au₃₈(SCH₂CH₂Ph)₂₄]. The bcc nanocluster has a distinct HOMO–LUMO gap of ca. 1.5 eV, much larger than the gap (0.9 eV) of the bi‐icosahedral [Au₃₈(SCH₂CH₂Ph)₂₄]. The unique structure of the bcc gold nanocluster may be promising in catalytic applications.     

An Unprecedented Kernel Growth Mode and Layer‐Number‐Odevity‐Dependent Properties in Gold Nanoclusters

Kernel atoms of Au nanoclusters are packed layer‐by‐layer along the [001] direction with every full (001) monolayer composed of 8 Au atoms (Au₈ unit) in nanoclusters with formula of Au_8n+4(TBBT)_4n+8 (n is the number of Au₈ units; TBBTH=4‐tert‐butylbenzenelthiol). It is unclear whether the kernel atoms can be stacked in a defective‐layer way along the [001] direction during growth of the series of nanoclusters and how the kernel layer number affects properties. Now, a nanocluster is synthesized that is precisely characterized by mass spectrometry and single‐crystal X‐ray crystallography, revealing a layer stacking mode in which a half monolayer composed of 4 atoms (Au₄ unit) is stacked on the full monolayer along the [001] direction. The size and the odevity of the kernel layer number influence the properties (polarity, photoluminescence) of gold nanoclusters. The obtained nanocluster extends the previous formula from Au_8n+4(TBBT)_4n+8 to Au_4n+4(TBBT)_2n+8 (n is the number of Au₄ units).     

Au2PbP2, Au2TlP2, and Au2HgP2: Ternary Gold Polyphosphides with Lead, Thallium, and Mercury in the Oxidation State Zero

The polyphosphide Au₂PbP₂ was prepared by reaction of the elemental components using liquid lead as a reaction medium. Well-developed crystals were obtained after dissolving the matrix in hydrochloric acid. Their crystal structure was determined from four-circle X-ray diffractometer data: Cmcm, a=323.6(1) pm, b=1137.1(2) pm, c=1121.8(1) pm, Z=4, R=0.023 for 478 structure factors and 20 variable parameters. The structure contains zigzag chains of phosphorus atoms with a typical single-bond distance of 219.4(2) pm. The two different kinds of gold atoms are both in linear phosphorus coordination with typical single-bond distances of 232.6(2) and 234.2(2) pm, and the lead atoms have only metal neighbors (7 Au and 2 Pb). Accordingly, chemical bonding of the compound may be expressed by the formula (Au⁺¹)₂Pb^±0(P⁻¹)₂. The corresponding thallium and mercury polyphosphides Au₂TlP₂ (a=324.1(1) pm, b=1136.1(1) pm, c=1122.1(1) pm) and Au₂HgP₂ (a=322.1(1) pm, b=1131.4(2) pm, c=1122.6(1) pm) were found to be almost isotypic with Au₂PbP₂. Their crystal structures were refined from single-crystal X-ray data to R=0.036 (682 F values, 25 variables) and R=0.026 (539 F values, 35 variables), respectively. The structure of these compounds may also be described as consisting of a three-dimensional network of condensed 8- and 10-membered Au₂P₆ and Au₄P₆ rings forming parallel channels, which are filled by the lead, thallium, and mercury atoms. The lead atoms are well localized in these channels, while the thallium and even more the mercury atoms occupy additional positions within these channels. Freshly prepared samples of Au₂HgP₂ show reproducibly slightly different axial ratios and larger cell volumes (ΔV=0.5%) than those after exposure of the samples to air for several days.     

An Unprecedented Kernel Growth Mode and Layer-Number-Odevity-Dependent Properties in Gold Nanoclusters

Kernel atoms of Au nanoclusters are packed layer-by-layer along the [001] direction with every full (001) monolayer composed of 8 Au atoms (Au₈ unit) in nanoclusters with formula of Au_8n+4(TBBT)_4n+8 (n is the number of Au₈ units; TBBTH=4-tert-butylbenzenelthiol). It is unclear whether the kernel atoms can be stacked in a defective-layer way along the [001] direction during growth of the series of nanoclusters and how the kernel layer number affects properties. Now, a nanocluster is synthesized that is precisely characterized by mass spectrometry and single-crystal X-ray crystallography, revealing a layer stacking mode in which a half monolayer composed of 4 atoms (Au₄ unit) is stacked on the full monolayer along the [001] direction. The size and the odevity of the kernel layer number influence the properties (polarity, photoluminescence) of gold nanoclusters. The obtained nanocluster extends the previous formula from Au_8n+4(TBBT)_4n+8 to Au_4n+4(TBBT)_2n+8 (n is the number of Au₄ units).     

Au108S24(PPh3)16: A Highly Symmetric Nanoscale Gold Cluster Confirms the General Concept of Metalloid Clusters

The reduction of (Ph₃P)AuCl with NaBH₄ in the presence of HSC(SiMe₃)₃, leads to one of the largest metalloid gold clusters: Au₁₀₈S₂₄(PPh₃)₁₆ ( 1 ). Within 1 an octahedral Au₄₄ core of gold atoms arranged as in Au metal is surrounded by 48 oxidized Au atoms of an Au₄₈S₂₄ shell, a novel building block in gold chemistry. The protecting Au₄₈S₂₄ shell is completed by additional 16 Au(PPh₃) units, leading to a complete protection of the gold core. Within 1 the Au–Au distances get more molecular on going from the center to the ligand shell. Cluster 1 represents novel structural motives in the field of metalloid gold clusters which also are partly typical for metal atoms in metalloid clusters: M_n R_m (n >m ).     

An Inherently Chiral Au24 Framework with Double‐Helical Hexagold Strands

2,3‐bis(diphenylphosphino)butane enantiomers (chiraphos, L) used as chiral auxiliaries results in the preferential formation of an unprecedented Au₂₄ framework with inherent chirality. The crystal structure of [Au₂₄L₆Cl₄]²⁺ ( 1 ) has a square antiprism‐like octagold core twinned by two helicene‐like hexagold motifs, where the inherent chirality is associated with the helical arrangement. The clusters carrying (R,R)‐ and (S,S)‐ diphosphines had right‐ and left‐handed strands, respectively. Circular dichroism spectra showed peaks in the visible to near‐IR region, some of which did not coincide with absorption bands, suggesting the enantiomeric Au₂₄ frameworks possess unique chiroptical properties. The Au₂₄ frameworks were thermally robust, which could be attributed to the superatomic concept (18 e^? system) and the steric constraint effects of the bridging ligand units.     

Synthesis, Chemical Characterization, and Molecular Structure of Au8{Fe(CO)4}4(dppe)2 and Au6Cu2{Fe(CO)4}4(dppe)2

The new Au₈{Fe(CO)₄}₄(P^P)₂ and Au₆Cu₂{Fe(CO)₄}₄(P^P)₂ (P^P=dppm, dppe) neutral cluster compounds were isolated in good yields by condensation of the [Au₃{Fe(CO)₄}₂(P^P)]^- anions with Au(SEt₂)Cl and CuCl, respectively, and have been characterized by IR, NMR and microanalyses. The molecular structures of Au₈{Fe(CO)₄}₄(dppe)₂ and Au₆Cu₂{Fe(CO)₄}₄(dppe)₂ have been determined by X-ray diffraction studies. Both molecules adopt a stereogeometry of the heavy atoms consisting of a triangulated and corrugated ribbon twisted around the elongation direction. Contrary to the expectations the latter displays the two copper atoms in the sites of highest connectivity. This implies that site exchange between copper and gold occurs during the synthesis.     

Solvothermal Synthesis, Crystal Structure Determination, and Properties of the Thioantimonate [Ph4P]2[Sb6S10]

 The reaction of elemental antimony with elemental sulfur and [Ph₄P]Br in an aqueous solution of neopentanediamine under solvothermal conditions yields yellow needles of the new thioantimonate(III) [Ph₄P]₂[Sb₆S₁₀]. The structure consists of [Ph₄P]⁺ cations and infinite one-dimensional anionic (Sb₆S₁₀ ²⁻)_n chains running along the crystallographic a axis. The chains are composed of 10-membered Sb₅S₅ rings with alternating Sb and S atoms and separated by the tetraphenylphosphonium cations. Upon heating the compound decomposes in two distinct steps, starting at about 100°C. The final product was identified by X-ray powder diffractometry as Sb₂S₃.     

Superoxide Formation on Isolated Cationic Gold Clusters

Gold nanoparticles are known to be highly versatile oxidation catalysts utilizing molecular oxygen as a feedstock, but the mechanism and species responsible for activating oxygen remain unclear. The reaction between unsupported cationic gold clusters and molecular oxygen has been investigated. The resulting complexes were characterized in the gas phase using IR spectroscopy. A strong red‐shift in the observed ν(O‐O) stretching frequency indicates the formation of superoxo (O₂^?) moieties. These moieties are seen to form spontaneously in systems, which upon electron transfer attain a closed shell within the spherical jellium model (Au₁₀⁺ and Au₂₂⁺), whereas an oxygen induced self‐promotion in the activation is observed for other systems (Au₄⁺, Au₁₂⁺, Au₂₁⁺).     

Role of Gold in Inflammation and Tristetraprolin Activity

The zinc finger protein tristetraprolin (TTP) regulates inflammation by downregulating cytokine mRNAs. Misregulation results in arthritis, sepsis and cancer, and there is an interest in modulating TTP activity with exogenous agents. Gold has anti-inflammatory properties and has recently been shown to modulate the signaling pathway that produces TTP, suggesting that TTP may be a target of gold. The reactivity of [Au^III(terpy)Cl]Cl₂ with TTP was investigated by UV/Vis spectroscopy, spin-filter inductively coupled plasma mass spectrometry, X-ray absorption spectroscopy and native electrospray ionization mass spectrometry. Au^III was found to replace zinc in the protein active site in the reduced Au^I form, with the Au^I ion coordinated to two cysteine residues in a linear geometry. The replacement of Zn^II with Au^I results in loss of both secondary structure and RNA binding function. In contrast, when Zn^IITTP is bound to its RNA target, no replacement of Zn^II with Au^I is observed, even in the presence of excess Au^IIIterpy. This discovery of differential reactivity of gold with TTP versus TTP/RNA offers a potential strategy for selective targeting with gold complexes to control inflammation.     

Giant Emission Enhancement of Solid‐State Gold Nanoclusters by Surface Engineering

Ligand‐induced surface restructuring with heteroatomic doping is used to precisely modify the surface of a prototypical [Au₂₅(SR¹)₁₈]^? cluster ( 1 ) while maintaining its icosahedral Au₁₃ core for the synthesis of a new bimetallic [Au₁₉Cd₃(SR²)₁₈]^? cluster ( 2 ). Single‐crystal X‐ray diffraction studies reveal that six bidentate Au₂(SR¹)₃ motifs (L2) attached to the Au₁₃ core of 1 were replaced by three quadridentate Au₂Cd(SR²)₆ motifs (L4) to create a bimetallic cluster 2 . Experimental and theoretical results demonstrate a stronger electronic interaction between the surface motifs (Au₂Cd(SR²)₆) and the Au₁₃ core, attributed to a more compact cluster structure and a larger energy gap of 2 compared to that of 1 . These factors dramatically enhance the photoluminescence quantum efficiency and lifetime of crystal of the cluster 2 . This work provides a new route for the design of a wide range of bimetallic/alloy metal nanoclusters with superior optoelectronic properties and functionality.     

Nanoceria Supported Gold Catalysts for CO Oxidation

Two types of CeO₂ nanocubes (average size of 5 and 20 nm, respectively) prepared via the hydrothermal process were selected to load gold species via a deposition‐precipitation (DP) method. Various measurements, including X‐ray diffraction (XRD), Raman spectra, high resolution transmission electron microscopy (HRTEM), in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS), and temperature‐programmed reduction by hydrogen (H₂‐TPR), were applied to characterize the catalysts. It is found that the sample with ceria size of 20 nm (Au/CeO₂‐20) was covered by well dispersed both Au³⁺ and Au^δ+ (0 < δ < 1). For the other sample with ceria size of 5 nm (Au/CeO₂‐5), Au³⁺ is the dominant gold species. Au/CeO₂‐20 performed better catalytic activity for CO oxidation because of the strong CO adsorption of Au^δ+ in the catalysts. The catalytic activity of Au/CeO₂‐5 was improved due to the transformation of Au³⁺ to Au^δ+. Based on the CO oxidation and in situ DRIFTS results, Au^δ+ is likely to play a more important role in catalyzing CO oxidation reaction.     

Gold(I)‐Catalyzed Enantioselective Intermolecular Hydroarylation of Allenes with Indoles and Reaction Mechanism by Density Functional Theory Calculations

Chiral binuclear gold(I) phosphine complexes catalyze enantioselective intermolecular hydroarylation of allenes with indoles in high product yields (up to 90 %) and with moderate enantioselectivities (up to 63 % ee). Among the gold(I) complexes examined, better ee values were obtained with binuclear gold(I) complexes, which displayed intramolecular Au^I Au^I interactions. The binuclear gold(I) complex 4c [(AuCl)₂( L3 )] with chiral biaryl phosphine ligand (S)‐(−)‐MeO‐biphep ( L3 ) is the most efficient catalyst and gives the best ee value of up to 63 %. Substituents on the allene reactants have a slight effect on the enantioselectivity of the reaction. Electron‐withdrawing groups on the indole substrates decrease the enantioselectivity of the reaction. The relative reaction rates of the hydroarylation of 4‐X‐substituted 1,3‐diarylallenes with N‐methylindole in the presence of catalyst 4c [(AuCl)₂( L3 )] / AgOTf [ L3 =(S)‐(−)‐MeO‐biphep], determined through competition experiments, correlate (r²=0.996) with the substituent constants σ. The slope value is −2.30, revealing both the build‐up of positive charge at the allene and electrophilic nature of the reactive Au^I species. Two plausible reaction pathways were investigated by density functional theory calculations, one pathway involving intermolecular nucleophilic addition of free indole to aurated allene intermediate and another pathway involving intramolecular nucleophilic addition of aurated indole to allene via diaurated intermediate E2 . Calculated results revealed that the reaction likely proceeds via the first pathway with a lower activation energy. The role of Au^I Au^I interactions in affecting the enantioselectivity is discussed.     

Well‐Defined Dinuclear Gold Complexes for Preorganization‐Induced Selective Dual Gold Catalysis

The synthesis, reactivity, and potential of well‐defined dinuclear gold complexes as precursors for dual gold catalysis are explored. Using the preorganizing abilities of the ditopic PN^HP^iPr ( L^H ) ligand, dinuclear Au^I–Au^I complex 1 and mixed‐valent Au^I–Au^III complex 2 provide access to structurally characterized chlorido‐bridged cationic species 3 and 4 upon halide abstraction. For 2 , this transformation involves unprecedented two‐electron oxidation of the redox‐active ligand, generating a highly rigidified environment for the Au₂ core. Facile reaction with phenylacetylene affords the σ,π‐activated phenylacetylide complex 5 . When applied in the dual gold heterocycloaddition of a urea‐functionalized alkyne, well‐defined precatalyst 3 provides high regioselectivities for the anti‐Markovnikov product, even at low catalyst loadings, and outperforms common mononuclear Au^I systems. This proof‐of‐concept demonstrates the benefit of preorganization of two gold centers to enforce selective non‐classical σ,π‐activation with bifunctional substrates.     

Template Synthesis,Metalation, and Self‐Assembly of Protic Gold(I)/(NHC)2 Tectons Driven by Metallophilic Interactions

A new protocol for the synthesis of protic bis(N‐heterocyclic carbene) complexes of Au^I by a stepwise metal‐controlled coupling of isocyanide and propargylamine is described. They are used as tectons for the construction of supramolecular architectures through metalation and self‐assembly. Notably a unique polymeric chain of Cu^I with alternate Au^I/bis(imidazolate) bridging scaffolds and strong unsupported Cu^I–Cu^I interactions has been generated, as well as a 28‐metal‐atoms cluster containing a nanopiece of Cu₂O trapped by peripheral Au^I/bis(imidazolate) moieties.     

(AsPh4)2[(μ-N2S2) (VCI5)2] Synthese,IR-Spektrum und Kristallstruktur

(AsPh₄)₂[(μ-N₂S₂)(VCl₅)₂]. Synthesis, I.R. Spectrum, and Crystal Structure From the reaction of VCl₄ and S₃N₂Cl₂ in CCl₄ solution a solid, black product mixture is obtained. From this, the title compound can be extracted by reaction with AsPh₄Cl in CH₂Cl₂ solution. It can also be synthesized from AsPh₄VCl₅ and S₃N₃Cl₃ in CH₂Cl₂ solution. The i.r. spectra of (AsPh₄)₂[(μ-N₂S₂)(VCl₅)₂] (black crystal plates) and AsPh₄VCl₅ (brown needles) are reported. The crystal structure of (AsPh₄)₂[(μ-N₂S₂)(VCl₅)₂] was determined by X-ray diffraction. It crystallizes in the monoclinic space group P2₁/c with two formula units per unit cell. The lattice constants are a = 1113.9, b = 1712.8, c = 1508.8 pm, β = 106.68°. The centrosymmetric [(μ-N₂S₂)(VCl₅)₂]^2? ion consists of two quadratic-pyramidal VCl₅ units which are linked via the N atoms of a N₂S₂ ring. The N₂S₂ ring shows positional disorder in two different orientations in the crystal. The AsPh₄⊕ ions form (AsPh₄⊕)₂ pairs via inversion centers, each pair is surrounded by eight anions.