Cluster chemistry: XXXIX. Gold—ruthenium clusters with sulphur ligands: Synthesis and structure of HRu3Au(μ3-S)(CO)9(PPh3), Ru3Au(μ3-SBut)(CO)9(PPh3) and Ru3Au2(μ3-S)(CO)9(PPh3)2

H₂Ru₃(μ₃-S)(CO)₉ is deprotonated by K[HBBu^s₃] to give cluster anions which react with [O{Au(PPh₃)}₃]⁺ or with AuCl(PPh₃)/T1⁺ to give HRu₃Au(μ₃-S)(CO)₉(PPh₃) (1) and Ru₃Au₂(μ₃-S)(CO)₉(PPh₃)₂ (3). A similar sequence with HRu₃(μ₃-SBu^t)(CO)₉ leads to Ru₃Au(μ₃-SBu^t)(CO)₉(PPh₃) (2) as the main product although some 1 also forms, indicating SC cleavage competes with deprotonation of HRu₃(μ₃-SBu^t)(CO)₉ by [HBBu^s₃]^?. The X-ray crystal structures of 1, 2 and 3 are described; (1) and (2) have “butterfly” AuRu₃ cores with markedly different hinge angles of 119 and 148° respectively, while 3 has a trigonal-bipyramidal Au₂Ru₃ skeleton. All three clusters have the sulphur atom symmetrically bridging the Ru₃ triangular face.     

Cluster chemistry: XXX. Reaction of a triruthenium anion with [O{Au(PPh3)}3][BF4]: Synthesis and structure of Ru3Au3(μ3-2η1,η3-C12H15)(CO)8(PPh3)3

The cluster HRu₃(μ₃-C₁₂H₁₅)(CO)₉ is rapidly deprotonated by K[HBBu₃^sec] in tetrahydrofuran, generating the anion [Ru₃(μ₃-C₁₂H₁₅)(CO)₉]^? in high yield. Reaction between this anion and [O{Au(PPh₃)}₃][BF₄] gives Ru₃Au₃(μ₃-C₁₂H₁₅)(CO)₈(PPh₃)₃ (2) as the main product, shown by an X-ray study to contain a capped trigonal-bipyramidal Ru₃Au₃ core in which the C₁₂H₁₅ ligand is bonded in the μ₃-2η¹,η³ fashion to the Ru₃ face. An alternative formulation involving the cyclo-Au₃(PPh₃)₃ moiety acting as a three-electron donor to the Ru₃ cluster is discussed. Crystals of 2 are monoclinic, space group P2₁/c, a 13.574(1), b 40.634(4), c 14.617(2) Å, β 92.58(1)°, Z = 4; 3233 data with I > 3σ(I) were refined to R = 0.078, R_w = 0.084.     

Cluster chemistry: XXXIII. Reactions of [{Au(PPh3)}3O]+ with [Ru3(μ3-C2But)(CO)9]−: X-ray structure of [Ru3Au2(μ3-CCHBut)(CO)9(PPh3)2], containing a t-butylvinylidene ligand attached to a trigonal-bipyramidal Ru3Au2 core

Deprotonation (K[HBBu₃^s]) of HRu₃(μ₃-C₂Bu^t)(CO)₉, followed by reaction of the anion with [O{Au(PPh₃)}₃][BF₄], afforded the known complex Ru₃Au(μ₃-C₂Bu^t)(CO)₉ (9%), the vinylidene cluster Ru₃Au₂(μ₃-CCHBu^t)(CO)₉(PPh₃)₂ (16%) and the hexanuclear Ru₃Au₃(C₂Bu^t)(CO)₈(PPh₃)₃ (3%). The X-ray structure of the pentanuclear complex shows an asymmetric trigonal-bipyramidal Ru₃Au₂ core (Ru, Au at the apices) with the Ru₃ face bridged by a t-butylvinylidene ligand, being σ-bonded to Ru(1) and Ru(3), and η²-coordinated to Ru(2). Crystals are monoclinic, space group P2₁/n with a 19.121(3), b 13.109(3), c 23.649(4) Å, β 106.76(2)° and Z = 4. The structure was solved using 4405 observed diffractometer data, and refined to R 0.044, R_w 0.047.     

Synthesis of bridged and linked ruthenium and osmium carbonyl clusters containing a [Au2(Ph2PCH2CH2PPh2)]2+ unit. The crystal and molecular structures of Ru5C(CO)14Au2(Ph2PCH2CH2PPh2) and {Os4H3(CO)12}2Au2(Ph2PCH2CH2PPh2)

Treatment of Au₂(Ph₂PCH₂CH₂PPh₂)Cl₂ with one equivalent of the [Ru₅C(CO)₁₄]²⁻ dianion in the presence of TlPF₆ gives Ru₅C(CO)₁₄Au₂(Ph₂PCH₂CH₂PPh₂) (1) in good yield and the [{Ru₅C(CO)₁₄}₂Au₂(Ph₂PCH₂CH₂PPh₂)]²⁻ (2) anion in low yield. Complex 2 becomes the major product if 2 equivalents of [Ru₅C(CO)₁₄]²⁻ are used. Reaction of [Au₂(Ph₂PCH₂CH₂PPh₂)Cl₂] with 3 equivalents of [H₃Os₄(CO)₁₂]⁻ anion in the presence of TlPF₆ affords {H₃Os₄(CO)₁₂}₂Au₂(Ph₂PCH₂CH₂PPh₂) (3) in reasonable yield. X-ray diffraction studies of 1 and 3 show that they contain the [Au₂(Ph₂PCH₂CH₂PPh₂)]²⁺ fragment in different coordination modes.     

Gold clusters: synthesis and characterization of [Au8(PPh3)7(CNR)]2+, [Au9(PPh36(CNR2]3+ and [Au11(PPH37(CNR)2O]2+ and their reactivity towards amines. The crystal structure of [Au11(PPh3)7(CN-i-Pr)2I](PF6)2

In the reactions of [Au₈(PPh₃)₇]²⁺, [Au₈(PPh₃)₈]²⁺ and [Au₉(PPh₃)₈]³⁺ with RNC (R = isopropyl and t-butyl) in dichloromethane [Au₈(PPh₃)₇CNR]²⁺ is initially, and is then converted into [Au₉(PPh₃)₆(CNR)₂]³⁺ via various intermediates. [Au₉(PPh₃)₆(CNR)₂]³⁺ reacts with I⁻ at low temperature (−78°C) in methanol to yield [Au₁₁(PPh₃)₇(CNR)₂I]²⁺, but when the reaction is carried out at room temperature Au₁₁ (PPh₃)₆(CNR)I₃ is formed. The cluster compounds have been characterised by elemental analysis, ³¹P{¹H} NMR, conductivity measurements, IR and ¹⁹⁷Au Mössbauer spectroscopy. The reactions of the clusters with amines to form carbene clusters are very slow, and the reasons for this are considered.The structure of [Au₁₁C₁₃₄H₁₁₂IN₂P₇](PF₆ was determined by X-ray diffraction. M_r = 3796.39 cubic, space group 143_d, a 37.955(12) Å, V 54677.2 ų, Z = 16, D_c = 2.21 Mg m⁻³, Mo-K_α radiation (graphite crystal monochromator, λ 0.71069 Å), μ(Mo-K_α) 125.2 cm⁻¹, F(000) = 33510.3, T 293 K. Final conventional R-factor = 0.048, R_w = 0.062 ofr 1867 unique reflections and 198 variables. The Au-skeleton is the same as in Au₁₁(PPh₃)₈I₃ having C_3v symmetry with one central and 10 peripheral Au atoms.     

Cluster Chemistry: XXVIII. Utility of fast atom bombardment mass spectrometry for the characterisation of high molecular weight complexes containing metal clusters

Fast atom bombardment (FAB) mass spectrometry has been used to obtain spectra of HRu₃Au(μ₃-S)(CO)₉(PPh₃), Ru₃Au₂(μ₃-S)(CO)₉(PPh₃)₂ and Ru₃Au₃(μ₃-C₁₂H₁₅)(CO)₈(PPh₃)₃, none of which give metal-containing ions in conventional EI mass spectrometry. All the compounds give molecular (M⁺) or quasimolecular ([M + 2H]⁺) ions which fragment by conventional routes.     

The reaction of Ru3(CO)12 with HC9PPh2)3. Characterisation of Ru3(CO)9[HC(PPh2)3], and crystal and molecular structure of Ru3(CO)9[HC(PPh2)(PhPC6H4PPh)]·CHCl3

Reaction of Ru₃(CO)₁₂ with HC(PPh₂)₃ leads to a variety of products, two of which have been characterised. One is the symmetrically capped product Ru₃(CO)₉[HC(PPh₂)₃], which was characterised spectroscopically. The second product was characterised crystallographically as Ru₃(CO)₉[HC(PPh₂)-(PhPC₆H₄PPh)]-CHCl₃.     

Synthesis of palladium-tin carbonylphosphine clusters and X-ray study of the Pd3Sn2(acac)4(CO)2(PPh3)3 cluster

It has been shown for the first time that the reaction of bi-valent tin acetyl-acetonate with palladium carbonylphosphine clusters, Pd₄(CO)₅(PPh₃)₄ (I), Pd₄(CO)₅(PEt₃)₄ (II) and Pd₃(CO)₃(PPh₃)₄ (III), results in the formation of heterometal pentanuclear clusters of general formula Pd₃Sn₂(acac)₄(CO)₂(PR₃)₃; R  Ph (IV), Et (V). X-ray analysis of Pd₃Sn₂(acac)₄(CO)₂(PPh₃)₃ at 20°C (λ(Mo), 4396 reflections, space group P2₁/n, Z = 4, R = 0.037) shows that IV in the form of the crystalline hydrate, Pd₃Sn₂(acac)₄(CO)₂(PPh₃)₃ · χH₂O (χ ∼ 1), contains a distorted “propeller”-shaped Pd₃Sn₂ metal frame with PdSn distances of 2.679–2.721(1) Å; two short PdPd bonds, 2.708 and 2.720(1) Å, bridged by μ₂-CO ligands, and an elongated central Pd(1)Pd(2) bond of 2.798 Å. Sn atoms have distorted octahedral coordination, the dihedral angles formed by Pd₃ moieties and two Pd₂Sn triangles are 127.6 and 106.5°; and the angle between Pd₂Sn moieties is 126.0°.     

Synthesis and molecular structure of [Au3Ru4(μ3-H)(CO)12(PPh3)3]

The title compound can be prepared in good yield by heating either [Ru₄(μ-H)₄(CO)₁₂] or [Au₂Ru₄(μ₃-H)₂(CO)₁₂(PPh₃)₂] with [AuMe(PPh₃)] in toluene. The related compound [Au₃Ru₄(μ₃-H)(μ-dppm)(CO)₁₂(PPh₃)] has also been prepared. Both trigoldtetraruthenium clusters undergo dynamic behaviour in solution, involving intramolecular rearrangement of the metal core, as revealed by variable temperature NMR studies. The crystal structure of [Au₃Ru₄(μ₃-H)(CO)₁₂(PPh₃)₃] has been established by an X-ray diffraction study. The metal atom core comprises a trigonal bipyramidal AuRu₄ unit with two AuRu₂ faces capped by gold atoms.     

Synthesis and structural characterisation of [Au2Pt2(PPh3)4(CN-xylyl)4](PF6)2: A platinum—gold cluster with a flattened butterfly geometry

[Au₂Pt₂(PPh₃)₄(CN-xylyl)₄](PF₆)₂ (CN-xylyl = 2,6-dimethylphenylisocyanide) has been synthesised from [Pt(C₂H₄)(PPh₃)₂] and [Au(CN-xylyl)₂]⁺ in CH₂Cl₂ and in the presence of an excess of CN-xylyl. A single crystal X-ray diffraction study has demonstrated that the metal atoms define a flattened butterfly with the gold atoms occupying the higher connectivity sites and forming a short bond of length 2.590(2) Å. The platinum—gold distances lie in the range 2.710(2)–3.026(2) Å.     

Dreizentren-oxidative Addition von Phosphor-Yliden an Ru3(CO)12

Three-Centre Oxidative Addition of Phosphorus Ylides to Ru₃(CO)₁₂ Phosphorus ylides undergo oxidative addition to Ru₃(CO)₁₂ to yield a wide range of Ru₃ clusters with triply bridging organic ligands derived from the ylides. Ph₃PCH₂ forms HRu₃(CO)₉(μ₃1-Ph₃P — CH — CO) ( 1 ) containing a phosphonio enolate. Ph₃PCH — CHO yields a product mixture containing the phosphonio enolate-bridged cluster and its PPh₃ derivative 6 , the phosphoniomethylidyne-bridged compound H₂Ru₃(CO)₉(μ₃1-C — PPh₃) ( 5 ), and the ketenylidene-bridged compound H₂Ru₃(CO)₈(PPh₃)(μ₃1-C — CO) ( 7 ). Thermal treatment converts the phosphonio enolate ligand (in 1 ) into the phosphoniomethylidyne ligand (in 5 ), and the latter into the ketenylidene ligand (in 7 ). With Ph₃PCH — C(O)Me and Ru₃(CO)₁₂ ortho1-metalated Ru₃ derivatives 10, 11 of the phosphonio ketone R₃P — C — C(O)Me are produced, and likewise with Ph₃PCH — COOEt the ortho1-metalated derivative 12 of the phosphonio ester R₃P — C — CO₂Et. Me₃PCH — COOtBu is oxidatively added to form HRu₃(CO)₉(μ₃1-Me₃P — C — COOtBu) ( 13 ) bearing a phosphonio ester ligand. — The crystal structures of 6 and 13 are reported. The sequence of Ru₃ clusters and the bonding modes of the μ₃ ligands can be related to the surface reactions during Fischer-Tropsch catalysis.     

Photochemical reactions of (CO)2 (PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3

Conclusions The photochemical reactions of (CO)₂(PPh₃)MnC₅H₄Fe(CO)₂C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)₂C₅H₅ with PPh₃ gave the products of replacing the CO on the Fe atom by PPh₃: respectively (CO)₂(PPh₃)MnC₅H₄Fe (CO)(PPh₃)C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)(PPh₃)C₅H₅.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2813–2815, December, 1977.     

[cis‐{η2‐(Ph3PAu)2}Ph3PCr(CO)4]·THF,featuring the shortest known separation between two Au metal centres in a heteronuclear Au2M cluster

The title compound, tetra­carbonyl‐1κ⁴C‐tris­(tri­phenyl­phos­phino)‐1κP,2κP,3κP‐triangulo‐chromiumdigold(Au—Au)(2 Cr—Au) tetra­hydro­furan solvate, [Au₂Cr(C₁₈H₁₅P)₃(CO)₄]·C₄H₈O, is a stable isolobal analogue of the extremely labile [(η²‐H₂)CrL_n–1] molecular hydrogen complex (n = 6; L is a neutral ligand, e.g. CO or PPh₃), and features the shortest known separation [2.6937 (2) Å] between two Au atoms in a triangular heteronuclear metal‐cluster framework.     

Synthesis and characterisation of HRuRh3(CO)12. Crystal structures of HRuRh3(CO)12, HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2

A new ruthenium-rhodium mixed-metal cluster HRuRh₃(CO)₁₂ and its derivatives HRuRh₃(CO)₁₀(PPh₃)₂ and HRuCo₃(CO)₁₀(PPh₃)₂ have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh₃(CO)₁₂: monoclinic, space group P2₁/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh₃(CO)₁₀(PPh₃)₂·C₆H₁₄: triclinic, space group P$\text{1}$, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo₃(CO)₁₀(PPh₃)₂·CH₂Cl₂: triclinic, space group P$\text{1}$, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)₄^? and (Ru(CO)₃Cl₂)₂ tetrahydrofuran followed by acid treatment yields HRuRh₃(CO)₁₂ in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh₃(CO)₁₀(PPh₃)₂, which is closely related to HRuCo₃(CO)₁₀(PPh₃)₂ and HFeCo₃(CO)₁₀(PPh₃)₂. The phosphines are axially coordinated.     

Preparation and Characterization of an Unusual Di-Cobalt Complex; X-Ray Crystal Structure of Co(CO)2(μ-CO)(μ:η2,η4-C4Ph4)Co(CO)2(PPh3)

Reaction of [MoCo(CO)₅(PPh₃)₂(η⁵-C₅H₅)] (1) with diphenylacetylene in tetrahydrofuran at 50 °C yielded two heterobimetallic compounds, [MoCo(CO)₄.(PPh₃){μ-PhC ? CPh}(η⁵-C₅H₅)] (4) and [MoCo(CO)₅{μ-PhC ? CPh} (η⁵-C₅H₅)] (5). However, an unexpected product, Co(CO)₂(μ-CO)(μ:η₂,η⁴-C₄Ph₄)Co(CO)₂(PPh₃) (6), was observed while attempting to grow the crystals for structural determination of 4. The X-ray crystal structure of 6 was determined: triclinic, $ {\rm P}\bar 1 $, a = 11.654(2) Å, b = 12.864(2) Å, c = 13.854(2) Å, α = 89.67(2)°, β = 86.00(2)°, γ= 83.33(2)°, V = 2057.9(6) ų Z=2. In 6, two cobalt fragments are at apical and basal positions of the pseudo-pentagonal pyramidal structure, respectively. The electron count for the apical cobalt fragments is 20, which is rather unusual. It is believed that 6 was formed after the fragmentation and recombination of the fragmented species of 4.     

[Au(C6F5)3(PPh2H)]: A Precursor for the Synthesis of Gold(III) Phosphide Complexes

The covalent radius of Au ^I is about 0.07 Å smaller than that of Ag^I. This was determined from the crystal structures of the isostructural complexes [N(PPh₃)][{Au(C₆F₅)₃(μ-PPh₂)}₂M] (M=Au (structure shown in the picture), Ag). These mixed Au^III–M phosphides were synthesized from [Au(C₆F₅)₃(PPh₂H)], the first gold complex to contain a secondary phosphane.     

The reaction of Ru3(CO)12 and Os3(CO)12 with PH2Ph; the x-ray crystal structures of HRu3(CO)10(PHPh) and H2Ru3(CO)9(PPh)

Twelve new trinuclear complexes containing terminal PH₂Ph, edge-bridging PHPh and/or capping PPh ligands have been isolated from the reaction of M₃(CO)₁₂ (M = Ru or Os) with PH₂Ph in refluxing solvents. HRu₃(CO)₁₀(PHPh) (IIIa) crystallises in the monoclinic space group P2₁/c with a = 8.761(3), b = 11.402(4), c = 22.041(7) Å,β = 98.89(2)°, and Z = 4. The structure was solved by a combination of direct methods and Fourier difference techniques, and refined by blocked-cascade least squares to R = 0.027 for 3676 unique observed intensities. The X-ray analysis shows that one edge of the Ru₃ triangle is bridged by a hydride and the PHPh ligand, and that the phosphorus-bound hydrogen atom lies over the metal triangle and the phenyl group away from it. This provides an explanation for the ready formation of the capped species H₂Ru₃(CO)₉(PPh) (Va) on pyrolysis of the edge-bridged complex as opposed to the previously reported conversion of HOs₃(CO)₁₀(NHPh) to an orthometallated derivative under similar conditions. An X-ray analysis of H₂Ru₃(CO)₉-(PPh) (Va) confirms the capped geometry. the complex crystallises in the monoclinic space group P2₁/n with a = 9.323(4), b = 15.110(6), c = 45.267(15) Å,β = 91.84(3)°, and Z = 12. the structure was solved and refined using the same techniques as described previously. The final residual R is 0.061 for 4839 reflections. Some reactions of Va show that the phosphorous cap is difficult to displace and stabilises the molecule with respect to decomposition to non-cluster species.     

Reaction of alkenes with trans-MeOIr(CO)(PPh3)2. Crystal and molecular structure of the pentacoordinate alkoxy-alkene iridium(I) complex,MeOIr(CO)(PPh3)2(TCNE)

The reaction of trans-MeOIr(CO)(PPh₃)₂ with TCNE (tetracyanoethylene) gives rise to the stable adduct MeOIr(CO)(PPh₃)₂(TCNE), the structure of which has been determined via a single-crystal X-ray diffraction study. This complex crystallizes in the centrosymmetric orthorhombic space group Pbca (D¹⁵_2h; No. 61) with a 17.806(4), b 20.769(4), c 20.589(6) Å, V 7614(3) ų and Z = 8. Diffraction data (Mo-K_α, 2θ = 5–45°) were collected on a Syntex P2₁ automated four-circle diffractometer and the structure was solved and refined to R_F 6.2% for 3502 data with |F₀| > 3σ(|F₀|) (R_F 4.3% for those 2775 data with |F₀| > 6 σ(|F₀|)). The central iridium atom has a distorted trigonal bipyramidal coordination geometry in which the methoxy group (Ir-OMe 2.057(8) Å) and carbonyl ligand (Ir-CO 1.897(14) Å) occupy axial sites with ∠MeOIrCO 174.7(4)°. The two triphenylphosphine ligands occupy equatorial sites (IrP(1) 2.399(3), IrP(2) 2.390(3) Å, ∠P(1)IrP(2) 110.32(11)° and the TCNE ligand is linked in an η² “face-on” fashion with the olefinic bond parallel to the equatorial coordination plane (IrC(4) 2.176(10), IrC(7) 2.160(12) Å) and lengthened substantially from its value in the free olefin (C(4)C(7) 1.539(17) Å).     

Low oxidation state ruthenium chemistry : IV. The reactions of M(CO)2(PPh3)3 complexes (M = Fe,Ru) and the hydrogenation and isomerization of alkenes catalyzed by RuL(CO)2(PPh3)2 (L = H2, PPh3)

The complexes M(CO)₂(PPh₃)₃ (I, M = Fe; II, M = Ru) readily react with H₂ at room temperature and atmospheric pressure to give cis-M(H)₂(CO)₂(PPh₃)₂ (III, M = Fe;IV,M = Ru). I reacts with O₂ to give an unstable compound in solution, in a type of reaction known to occur with II which leads to cis-Ru(O₂)(CO)₂(PPh₃)₂(V). Even compound IV reacts with O₂ to give V with displacement of H₂; this reaction has been shown to be reversible and this is the first case where the displacement of H₂ by O₂ and that of O₂ by H₂ at a metal center has been observed. III and IV are reduced to M(CO)₃(PPh₃)₂ by CO with displacement of H₂; Ru(CO)₃- (PPh₃)₂ is also formed by treatment of IV with CO₂, but under higher pressure. Compounds II and IV react with CH₂CHCN to give Ru(CH₂CHCN)(CO)₂- (PPh₃)₂(VI) which reacts with H₂ to reform the hydride IV.cis-Ru(H)₂(CO)₂(PPh₃)₂(IV) has been studied as catalyst in the hydrogenation and isomerization of a series of monoenes and dienes. The catalysts are poisoned by the presence of free triphenylphosphine. On the other hand the ready exchange of H₂ and O₂ on the “Ru(CO)₂(PPh₃)₂” moiety makes IV a catalyst not irreversibly poisoned by the presence of air. It has been found that even Ru(CO)₂(PPh₃)₃(II) acts as a catalyst for the isomerization of hex-1-ene at room temperature under an inert atmosphere.     

Bis­[bis­(di­phenyl­phosphino­methyl)­phenyl­phosphine]­di­chloro­tetra­gold(I) bis­[chloro­tris­(penta­fluoro­phenyl)­aurate(III)]

The cation of the title compound, [Au₄(PPh₂CH₂PPhCH₂PPh₂)₂Cl₂][Au(C₆F₅)₃Cl]₂ or [Au₄Cl₂(C₃₂H₂₉P₃)₂][AuCl(C₆F₅)₃]₂, displays a rhomboidal geometry for the Au atoms, with short Au?Au distances of 3.104 (2) and 3.185 (1) Å; the linear coordination at the Au^I atoms is distorted: P—Au—P 164.7 (2)° and P—Au—Cl 170.67 (11)°. The anion shows the expected square‐planar geometry at Au^III, with the Au atom 0.022 (5) Å out of the plane of the four donor atoms.