Reactivity of the heteronuclear cluster Cp*IrOs3(μ-H)2(CO)10 with some group 16 substrates

The mixed metal cluster Cp*IrOs₃(μ-H)₂(CO)₁₀ (1) reacted readily with a number of group 16 substrates under chemical activation with TMNO. It reacted with C₆H₅SH to afford the novel cluster Cp*IrOs₃(μ-H)₃(CO)₉(μ-SPh) (2). It also reacted readily with Ph₃PSe to afford five new clusters, viz., Cp*IrOs₃(μ-H)₂(CO)₉(μ₃-Se) (3) Os₃(μ-H)₂(CO)₇(μ₃-Se)(PPh₃)₂ (4), Cp*IrOs₃(μ-H)₂(CO)₉(PPh₃) (5), Cp*IrOs₃(μ-H)₂(μ₃-Se)(CO)₈(PPh₃) (6) and Cp*IrOs₃(μ-H)₂(μ₃-Se)₂(CO)₇(PPh₃) (7). The reaction pathway for this reaction has been studied carefully and suggests that Ph₃PSe functioned primarily as a selenium atom transfer agent to give initially the even more reactive 3. The reaction of 1 with di-p-tolyl ditelluride yielded three new clusters, 8-10, which were non-interconverting stereoisomers with the formulation Cp*IrOs₃(μ-H)₂(μ-Te-p-C₆H₄CH₃)₂(CO)₈.     

Regiospecific insertion into the Co–Co bond of the mixed-metal cluster Co2Rh2(CO)12 by an electron-poor alkyne: X-ray diffraction structure of the butterfly cluster Co2Rh2(CO)10(μ-HCCCO2Me)

The reaction between the mixed-metal tetrahedral cluster Co₂Rh₂(CO)₁₂ (1) and the electron-poor alkyne methyl propiolate in hexane at room temperature furnishes a mixture of products consisting of Co₃Rh(CO)₁₂ (2), Co₃Rh(CO)₁₀(μ-HCCCO₂Me) (3), Co₂Rh₂(CO)₁₀(μ-HCCCO₂Me) (4), and CoRh₃(CO)₉(μ-HCCCO₂Me)₃ (5). The isolation and solution spectroscopic data of these compounds are described, and the solid-state structure of Co₂Rh₂(CO)₁₀(μ-HCCCO₂Me) determined by X-ray diffraction analysis. The title cluster crystallizes in the triclinic space group. The solid-state structure of Co₂Rh₂(CO)₁₀(μ-HCCCO₂Me) provides proof for the regiospecific insertion of the methyl propiolate ligand into the Co–Co bond of the starting cluster Co₂Rh₂(CO)₁₂. The stability of clusters 3 and 4 in the presence of added methyl propiolate is discussed.     

CO substitution in HRu3(CO)10(μ-COMe) by the unsaturated diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): Synthesis and reactivity studies of the face-capped cluster Ru3(CO)7(μ3-COMe)[μ-P(Ph)CC(PPh2)C(O)CH2C(O)]

The reaction of the methylidyne-bridged cluster HRu₃(CO)₁₀(μ-COMe) (1) with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) and Me₃NO furnishes HRu₃(CO)₈(μ-COMe)(bpcd) (2) and HRu₃(CO)₈(Ph₂PH)[μ-PPh₂CCC(O)CH₂C(O)] (3) as the major and minor products, respectively. The ¹H and ³¹P NMR data indicate that the bpcd ligand in 2 is chelated to one of the ruthenium atoms that is bridged by the hydride and methylidyne ligands. Thermolysis of 2 is accompanied by P-Ph bond cleavage and elimination of benzene to yield Ru₃(CO)₇(μ₃-COMe)[μ-P(Ph)CC(PPh₂)C(O)CH₂C(O)] (4). Compound 4 consists of a triangular ruthenium core that is face-capped by μ₃-COMe methylidyne and μ-P(Ph)CC(PPh₂)C(O)CH₂C(O) phosphido ligands. The kinetics for the conversion of 2 → 4 have been measured in toluene solvent over the temperature range 320-343 K, and based on the observed activation parameters and the inhibitory effect of added CO on the reaction, a rate-limiting step involving a dissociative loss of CO is supported. Heating 4 in the presence of H₂ afforded the phosphinidene-capped cluster H₃Ru₃(CO)₇(μ₃-PPh)[μ-CC(PPh₂)C(O)CH₂C(O)] (5). Crystallographic analysis of 5 has confirmed the loss of the methylidyne moiety and the cleavage of the phosphido PhP-C(dione) bond, and the presence of three edge-bridging hydrides is supported by ¹H NMR spectroscopy. The reaction of 4 with added PPh₃ and PMe₃ has been investigated; the uptake of a single phosphine ligand occurs regiospecifically at one of the phosphido-bound ruthenium centers to give Ru₃(CO)₆L(μ₃-COMe)[μ-P(Ph)CC(PPh₂)C(O)CH₂C(O)] (PPh₃, 6; PMe₃, 7). Compound 6 contains 48e- and exhibits a structural motif similar to that found in 4. Compound 7 readily adds a second PMe₃ ligand to yield the bis-substituted cluster Ru₃(CO)₆(PMe₃)₂(μ₂-COMe)[μ-P(Ph)CC(PPh₂)C(O)CH₂C(O)] (8). The solid-state structure of 8 confirms the loss of two ruthenium-ruthenium bonds and the conversion of the original face-capping μ₃-COMe ligand to a μ₂-COMe moiety that tethers two non-bonding ruthenium centers. The two PMe₃ ligands in 8 coordinate to the same ruthenium center, and the 9e- P(Ph)CC(PPh₂)C(O)CH₂C(O) ligand binds all three ruthenium atoms through the phosphine, phosphido, alkene, and carbonyl moieties. Near-UV irradiation of 8 leads to loss of CO and polyhedral contraction of the triruthenium frame to yield the 48e- cluster Ru₃(CO)₅(PMe₃)₂(μ₃-COMe)[μ-P(Ph)CC(PPh₂)C(O)CH₂C(O)] (9).     

Ditertiary phosphine derivatives of the heteronuclear cluster RuOs3(μ-H)2(CO)13

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (1) reacted readily with a number of ditertiary phosphines under chemical activation with trimethylamine-N-oxide. The solid-state and solution structures of these derivatives have been examined. Six structural types have been characterized crystallographically, including one in which a phenyl group migrates from the ditertiary phosphine ligand to the metal framework. There are many more isomers present in solution, most of which are rapidly inter-converting via hydride migrations.     

Reactivity of the heteronuclear cluster RuOs3(μ-H)2(CO)13 with indene

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (1) reacts with indene under thermal activation to afford the novel clusters RuOs₃(μ-H)(CO)₉(μ-CO)₂(η⁵-C₉H₇) (3), RuOs₃(μ-H)(CO)₉(μ₃,η⁵:η²:η²-C₉H₇) (4) and Ru₂Os₃(μ-H)(CO)₁₁(μ₃,η⁵:η²:η²-C₉H₇) (5), the latter two possessing indenyl ligands in the μ₃,η⁵:η²:η² bonding mode. Cluster 5 exists as a mixture of two isomers. The inter-relationship among the clusters has also been investigated.     

Reaction of the heteronuclear cluster RuOs3(μ-H)2(CO)13 with toluene

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (4) reacts with refluxing toluene to form the clusters Ru₂Os₃(μ-H)₂(CO)₁₆ (5) RuOs₃(CO)₉(μ-CO)₂(η⁶-C₆H₅Me) (6) and Ru₂Os₃(CO)₁₂(μ-CO)(η⁶-C₆H₅Me) (7). Cluster 5 exists as a mixture of five isomers. The inter-relationship among the clusters has also been investigated.     

Thiolate-bridged heterometallic complexes of manganese and platinum: Synthesis and molecular structures of (CO)4Mn(μ-SPh)Pt(PPh3)2, (CO)3(PPh3)Mn(μ-SPh)Pt(PPh3)(CO), and (CO)3Mn(μ-SPh)Pt(PPh3)(Dppm)

A reaction of the dimer [Mn(CO)₄(SPh)]₂ with (PPh₃)₂Pt(C₂Ph₂) gave the heterometallic complex (CO)₄Mn(μ-SPh)Pt(PPh₃)₂ (I) and its isomer (CO)₃(PPh₃)Mn(μ-SPh)Pt(PPh₃)(CO) (II). A reaction of complex I with a diphosphine ligand (Dppm) yielded the heterometallic complex (CO)₃Mn(μ-SPh)Pt(PPh₃)(Dppm) (III). Complexes I–III were characterized by X-ray diffraction. In complex I, the single Mn-Pt bond (2.6946(3) ?) is supplemented with a thiolate bridge with the shortened Pt-S and Mn-S bonds (2.3129(5) and 2.2900(6) ?, respectively). Unlike complex I, in complex II, one phosphine group at the Pt atom is exchanged for one CO group at the Mn atom. The Mn-Pt bond (2.633(1) ?) and the thiolate bridge (Pt-S, 2.332(2) ?; Mn-S, 2.291(2) ?) are retained. In complex III, the Mn-Pt bond (2.623(1) ?) is supplemented with thiolate (Pt-S, 2.341(2) ?; Mn-S, 2.292(2) 0?) and Dppm bridges (Pt-P, 2.240(1)?; Mn-P, 2.245(2) ?). Apparently, the Pt atom in complexes I–III is attached to the formally double bond , as in Pt complexes with olefins.     

Synthesis and structure of mixed-metal thiolate complex Cp′Cr(CO)2(μ-SBu)Pt(PPh3)2: Side-on-coordination of Cr-S double bond with platinum

The reaction of [Cp′Cr(CO)₂(μ-SBu)]₂ (1) (Cp′ = MeC₅H₄) with (PPh₃)₂Pt(PhCCPh) gives Cp′Cr(CO)₂(μ-SBu)Pt(PPh₃)₂ (2) which could be regarded as a product of the substitution of acetylene ligand at platinum by a monomeric chromium-thiolate fragment. According to the X-ray diffraction analysis 2 contains single Cr-Pt (2.7538(15)) and Pt-S (2.294(2) Å) bonds while Cr-S bond (2.274(3) Å) is shortened in comparison with ordinary Cr-S bonds (2.4107(4)-2.4311(4) Å) in 1. The bonding between Cr-S fragment and platinum atom is similar to the olefine coordination in their platinum complexes.     

Synthesis and molecular structure of [((CO)3RuBr2)2(μ-SePh)2Ru(CO)4] cluster with a Ru3Se2 chain core

Treatment of ruthenium carbonyl, [Ru₃(CO)₁₂] with phenylseleno tribromide PhSeBr₃ afforded a new triruthenium cluster, [(CO)₁₀Br₄Ru₃(μ-SePh)₂] (1). Its molecular structure was determined by single crystal XRD method (P2₁/c; a = 10.514(3) Å; b = 10.814(3) Å; c = 19.063(5) Å; β = 105.064(4)°; V = 2093.1(10) Å³) and shown to have two lateral Ru(CO)₃Br₂ units attached via two PhSe bridges to a Ru(CO)₄ center forming a chain-like Ru-Se-Ru-Se-Ru cluster core. This is in contrast with a recently reported reaction of PhTeBr₃ with [Ru₃(CO)₁₂] which formed a monomeric complex of ruthenium-dicarbonyl-dibromo fragment coordinating two PhTeBr ligands, [(CO)₂RuBr₂(PhTeBr)₂].     

Formation of the silylene-bridged complex Fe2(CO)6(μ2-SiCl2)3 from cis-Fe(CO)4(SiCl3)2: an experimental and computational study

Abstract  

Thermolysis of cis-Fe(CO)₄(SiCl₃)₂ results in the formation of the novel compound Fe₂(CO)₆(μ₂-SiCl₂)₃, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe₂(CO)₆(SiCl₂)₃, including CO dissociation and chlorine abstraction by a SiCl₃ radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.     

Oxidative addition of the Mo-Cl bond to the Pt0 complex. Synthesis and structure of Cp′Mo(μ-CO)2(C2Ph2)Pt2(PPh3)2(CO)Cl

A reaction of Cp′Mo(CO)₃Cl(Cp′ = MeC₅H₄) with (PPh₃)₂Pt(C₂Ph₂) gave the heterometallic cluster Cp′Mo(μ-CO)₂(C₂Ph₂)Pt₂(PPh₃)₂(CO)Cl (I) as the sole product. According to X-ray diffraction data, complex I contains single Pt-Mo bonds (2.7962(5) and 2.7699(5) ?) but no Pt-Pt bond (Pt…Pt 2.9746(3) ?). The coordinated diphenylacetylene molecule forms two Pt-C σ-bonds (2.054(6) and 2.083(5) ?) and a π-bond to the Mo atom (Mo-C 2.265(6) and 2.272(5) ?; C≡C 1.387(8) ?). Original Russian Text ? A.A. Pasynskii, I.V. Skabitskii, Yu.V. Torubaev, S.S. Shapovalo, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No. 6, pp. 410–413.     

[Cu(HIm)2(PPh3)2](BF4)的合成与晶体结构

A Cu(Ⅰ) complex with mix ligands [Cu(HIm)₂(PPh₃)₂](BF₄) was synthesized and characterized by elemental analysis, IRspectroscopy and X-ray diffraction crystallography. The crystal belongs to monoclinic system and P2₁/c space group, with cell parameters, a=1.2836(3)nm, b=1.5089(3)nm, c=2.0661(4)nm, α=90°, β=101.464(4)°,γ=90°, V=3.9219(13)nm³, Z=4 and D_c=1.374mg·m^-3. The Cu(Ⅰ) is coordinated by two Patoms from triphenylphosphine and two Natoms from imidazole to form the distorted tetrahedral geometry.     

Stable radical adducts of diisopropylphosphoryl radicals with fullerene complexes (η2-C60)Os(CO)(PPh3)2(CNBut) and (η2-C70)Os(CO)(PPh3)2(CNBut)

It was determined by ESR spectroscopy that the UV irradiation of toluene solutions containing Hg[P(O)(OPrⁱ)₂ and the complex (²-C₆₀)Os(CO)(PPh₃)₂(CNBu^t) produces six stable regioisomeric adducts of phosphoryl radicals with complexes, which are not demetallated under UV irradiation and do not dimerize in the absence of UV irradiation. This is caused by the addition of the phosphoryl radicals to the carbon atoms of fullerene localized near the metal-containing moiety. The addition of the phosphoryl radicals to (²-C₇₀)Os(CO)(PPh₃)₂(CNBu^t) gives rise to the formation of nine stable regioisomeric radical adducts. A comparison of the composition of regioisomers of the radical adducts of C₇₀ with the phosphoryl radicals, which were formed directly from C₇₀ and from the radical adducts of ²-C₇₀)Os(CO)(PPh₃)₂(CNBu^t) by the demetallation of the latter, revealed an orienting effect of the osmium-containing moiety on the addition of the phosphoryl radicals to the fullerene complex.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1968–1972, September, 2004.     

对苯二甲酸二丙炔醇酯与Co2(CO)8、Mo2Cp2(CO)4和RuCo2(CO)11的反应

室温下对苯二甲酸二丙炔醇酯分别与Co2CO8Mo2Cp2CO4和RuCo2CO11反应得到三个有机金属化合物C6H4pCO2CH2C2Hμ2Co2CO621、C6H4pCO2CH2C2H2RuCo2CO922和HC2CH2OCOC6H4pCO2CH2C2HμMo2Cp2CO43。研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2CO9>Co2CO6>Mo2CO4Cp2。化合物1的晶体衍射发现属三斜晶系空间群a=8.1392b=8.8083c=11.3433β=96.2606°V=773.443Z=1Dc=1.748g·cm-3R=0.0513wR=0.1266。     

Disulfido iron-manganese carbonyl cluster complexes: Synthesis, structure, bonding and properties of the radical CpFeMn2(CO)7(μ3-S2)2

Two new compounds CpFeMn₂(CO)₇(μ₃-S₂)₂ (2) and Cp₃Fe₃Mn(CO)₄(μ₃-S₂)₂(μ₃-S) (3) were obtained by the treatment of [CpFeMn(CO)₅(μ₃-S₂)]₂ (1) with CO at room temperature in the presence of room light. Compound 2 contains two triply bridging disulfido ligands on opposite sides of an open FeMn₂ triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements show that it is paramagnetic with one unpaired electron per formula equivalent. The electronic structure of 2 was established by DFT and Fenske-Hall (FH) molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital that is located principally on the iron atom. The cyclic voltammogram of 2 exhibits one reversible one-electron oxidation wave at +0.34 V and one irreversible one-electron reduction wave at −0.66 V vs. Ag/AgCl. Compound 3 contains three iron atoms and one manganese atom with two triply bridging disulfido ligands and one triply bridging sulfido ligand and has no unpaired electrons. The molecular structures of compounds 2 and 3 were established by single crystal X-ray diffraction analyses.     

Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(μ-S-pySH)2(PPh3)2] and [Ag2Br2(μ-S-pySH)2(PPh3)2] complexes

Reaction of silver(I) halides with PPh₃ in acetonitrile and then with pyridine-2-thione (pySH) chloroform (1:1:1 molar ratio) has yielded sulfur bridged dimers of general formula, [Ag₂X₂(μ-S-pySH)₂(PPh₃)₂] (X = Cl, 1, Br, 2). Both these complexes have been characterized using analytical data, NMR spectroscopy and single crystal X-crystallography. The central Ag₂S₂ cores form parallelograms with unequal Ag–S bond distances (2.5832(8), 2.7208(11) Å) in 1 and (2.6306(4), 2.6950(7) Å) in 2, respectively. The Ag?Ag contacts of compounds 1 and 2 are 3.8425(8) and 3.8211(4) Å, respectively. The angles around Ag (in the range 87.19(2)–121.71(2)° in 1 and 87.81(2)–121.53(2)° in 2) reveal highly distorted tetrahedral geometry. There are inter dimer π–π stacking interactions between pyridyl rings (inter ring distances of 3.498 and 3.510 Å in complexes 1 and 2, respectively). The solution state ³¹P NMR spectroscopy has shown the existence of both monomers and dimers. The studies reveal relatively weaker intramolecular –NH?Cl hydrogen bonding in case of AgCl vis-à-vis that in CuCl which favored both a monomer and a dimer with AgCl, and only a monomer with CuCl.     

Chemistry of vinylidene complexes. XVIII. Synthesis and molecular structure of the novel trinuclear μ3-vinylidene complex CpReFePt(μ3-CCHPh)(CO)6(PPh3)

The interaction between Cp(CO)₂RePt(μ-CCHPh)(PPh₃)₂ (1) and Fe₂(CO)₉ afforded the new heterometallic μ₃-vinylidene cluster CpReFePt(μ₃-CCHPh)(CO)₆(PPh₃) (2). An X-ray diffraction study shows the complex 2 possesses a trimetallic Re-Fe-Pt chain core. The bond lengths are Re-Fe 2.8221(8), Fe-Pt 2.5813(8) Å; the Re?Pt distance is 3.3523(7) Å; the bond angle Re-Fe-Pt is 76.55(3)°. The μ₃-CCHPh ligand is η¹-bound to the Re and Pt atoms and η²-coordinated to the Fe atom. The CC bond length is 1.412(4) Å. The Pt atom is coordinated by the PPh₃ and CO groups. Complex 2 is characterized by the IR and ¹H, ¹³C and ³¹P NMR spectra.     

Synthesis and characterization of the cluster complexes containing tetrahedral FeCrCo(μ3-S) cluster cores generated by isolobal displacement reactions. Crystal structures of (η-RC5H4)FeCrCo(μ3-S)(CO)8 (R=H, CO2Et) and FeCo2(μ3-S)2(CO)9

The monoanions (η⁵-RC₅H₄)(CO)₃Cr⁻ (1, R=H; 2, R=Me; 3, R=CO₂Et) reacted with tetrahedral cluster FeCo₂(μ₃-S)(CO)₉ to give single isolobal displacement products (η⁵-RC₅H₄)FeCrCo(μ₃-S)(CO)₈ (4, R=H; 5, R=Me; 6, R=CO₂Et) in 86-89% yields, whereas monoanion (η⁵-RC₅H₄)(CO)₃Cr⁻ (7, R=C(O)Me) reacted with FeCo₂(μ₃-S)(CO)₉ to afford the expected single isolobal displacement product (η⁵-RC₅H₄)FeCrCo(μ₃-S)(CO)₈ (8, R=C(O)Me) in 5% yield and an unexpected square pyramidal cluster FeCo₂(μ₃-S)₂(CO)₉ (9) in 45% yield. Similarly, the dianions [η⁵-C₅H₄CH₂(CH₂OCH₂)_nCH₂C₅H₄-η⁵][(CO)₃Cr⁻]₂ (10, n=1; 11, n=2; 12, n=3) reacted with two molecules of FeCo₂(μ₃-S)(CO)₉ to produce double isolobal displacement products [η⁵-C₅H₄CH₂(CH₂OCH₂)_nCH₂C₅H₄-η⁵][FeCrCo(μ₃-S)(CO)₈]₂ (13, n=1; 14, n=2; 15, n=3) in 32-36% yields, while treatment of dianion [η⁵-C₅H₄C(O)CH₂]₂[(CO)₃Cr⁻]₂ (16) with two molecules of FeCo₂(μ₃-S)(CO)₉ gave the unexpected square pyramidal cluster FeCo₂(μ₃-S)₂(CO)₉ (9) in 42% yield and the corresponding double isolobal displacement product [η⁵-C₅H₄C(O)CH₂]₂[FeCrCo(μ₃-S)(CO)₈]₂ (17) in 8% yield. Products 4-6, 8, 9, 13-15 and 17 were characterized by elemental analyses, IR and ¹H NMR spectroscopy, as well as for 4, 6 and 9 by X-ray diffraction techniques.     

Ruthenium cluster compounds containing 1,1′-bis(diphenylphosphino)ferrocene (dppf): an electrochemical analysis and the crystal structure of [Ru3(CO)11]2(μ-dppf)

The electrochemistry of 1,1′-bis(diphenylphosphino)ferrocene (dppf) derivatives of Ru₃(CO)₁₂ was investigated. Two known compounds [Ru₃(CO)₈(μ-dppf)₂ (1) and Ru₃(CO)₁₀dppf (2)] and a new compound [Ru₃(CO)₁₁(μ-dppf)Ru₃(CO)₁₁ (3)] were prepared. Compound 3 was characterized spectroscopically and an X-ray crystal structure was obtained. The reductive electrochemistry of 1 and 2 showed an irreversible reduction and a follow-up oxidation, similar to Ru₃(CO)₁₂. The electrochemistry of compound 3 showed two irreversible waves and a follow-up oxidation. A trend in the reduction potential vs. the number of coordinated phosphorus atoms was noted. The oxidative electrochemistry of 1-3 showed a dppf-based chemically reversible wave, and an irreversible wave similar to that of Ru₃(CO)₁₂. Trends were also noted between the oxidation potential and the number of coordinated phosphorus atoms.     

Spanning [Pt2(μ-S)2(PPh3)4] metalloligands with 1,4-dimercurated durene

Reaction of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] with 0.5 mol equivalents of durene-1,4-bis(mercuric acetate) [AcOHgC₆Me₄HgOAc] in methanol gives the polynuclear complex [{Pt₂(μ-S)₂(PPh₃)₄}₂(μ-1,4-C₆Me₄Hg₂)]²⁺, isolated as its and salts. Positive-ion ESI mass spectra indicate that [{Pt₂(μ-S)₂(PPh₃)₄}₂(μ-1,4-C₆Me₄Hg₂)]²⁺ undergoes fragmentation by successive loss of PPh₃ ligands, while the ESI mass spectrum of the salt showed additional ions [Pt₂(μ-S)₂(PPh₃)₄(HgC₆Me₄HgPh)]⁺ and [Pt₂(μ-S)₂(PPh₃)₄HgPh]⁺ as a result of phenyl transfer from to Hg. A single-crystal X-ray structure determination on [{Pt₂(μ-S)₂(PPh₃)₄}₂(μ-1,4-C₆Me₄Hg₂)](BPh₄)₂ shows that the cation crystallises on a centre of symmetry, with structural features that are comparable to those of the previously characterised complex [Pt₂(μ-S)₂(PPh₃)₄HgPh]BPh₄.