The arylation of [Pt2(μ-S)2(PPh3)4]

Routes to the synthesis of the mixed sulfide-phenylthiolate complex [Pt₂(μ-S)(μ-SPh)(PPh₃)₄]⁺ have been explored; reaction of [Pt₂(μ-S)₂(PPh₃)₄] with excess Ph₂IBr proceeds readily to selectively produce this complex, which was structurally characterised as its PF₆⁻ salt. Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with other potent arylating reagents (1-chloro-2,4-dinitrobenzene and 1,5-difluoro-2,4-dinitrobenzene) also produce the corresponding nitroaryl-thiolate complexes [Pt₂(μ-S){μ-SC₆H₂(NO₂)₂X}(PPh₃)₄]⁺ (X = H, F). The complex [Pt₂(μ-S)(μ-SPh)(PPh₃)₄]⁺ reacts with Me₂SO₄ to produce the mixed alkyl/aryl bis-thiolate complex [Pt₂(μ-SMe)(μ-SPh)(PPh₃)₄]²⁺, but corresponding reactions with the nitroaryl-thiolate complexes are plagued by elimination of the nitroaryl group and formation of [Pt₂(μ-SMe)₂(PPh₃)₄]²⁺. [Pt₂(μ-S)(μ-SPh)(PPh₃)₄]⁺ also reacts with Ph₃PAuCl to give [Pt₂(μ-SAuPPh₃)(μ-SPh)(PPh₃)₄]²⁺.     

Thallium(III) complexes of the metalloligands [Pt2(μ-S)2(PPh3)4] and [Pt2(μ-Se)2(PPh3)4]

Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with the diarylthallium(III) bromides Ar₂TlBr [Ar = Ph and p-ClC₆H₄] in methanol gave good yields of the thallium(III) adducts [Pt₂(μ-S)₂(PPh₃)₄TlAr₂]⁺, isolated as their salts. The corresponding selenide complex [Pt₂(μ-Se)₂(PPh₃)₄TlPh₂]BPh₄ was similarly synthesised from [Pt₂(μ-Se)₂(PPh₃)₄], Ph₂TlBr and NaBPh₄. The reaction of [Pt₂(μ-S)₂(PPh₃)₄] with PhTlBr₂ gave [Pt₂(μ-S)₂(PPh₃)₄TlBrPh]⁺, while reaction with TlBr₃ gave the dibromothallium(III) adduct [Pt₂(μ-S)₂(PPh₃)₄TlBr₂]⁺[TlBr₄]⁻. The latter complex is a rare example of a thallium(III) dihalide complex stabilised solely by sulfur donor ligands. X-ray crystal structure determinations on the complexes [Pt₂(μ-S)₂(PPh₃)₄TlPh₂]BPh₄, [Pt₂(μ-S)₂(PPh₃)₄TlBrPh]BPh₄ and [Pt₂(μ-S)₂(PPh₃)₄TlBr₂][TlBr₄] reveal a greater interaction between the thallium(III) centre and the two sulfide ligands on stepwise replacement of Ph by Br, as indicated by shorter Tl-S and Pt?Tl distances, and an increasing S-Tl-S bond angle. Investigations of the ESI MS fragmentation behaviour of the thallium(III) complexes are reported.     

Heterobimetallic platinum-bismuth aggregates derived from [Pt2(μ-S)2(PPh3)4]

The metalloligand [Pt₂(μ-S)₂(PPh₃)₄] reacts with Bi(S₂CNEt₂)₃ or Bi(S₂COEt)₃ in methanol to produce the orange cationic adducts [Pt₂(μ-S)₂(PPh₃)₄Bi(S₂CNEt₂)₂]⁺ and [Pt₂(μ-S)₂(PPh₃)₄Bi(S₂COEt)₂]⁺, respectively, isolated as their hexafluorophosphate salts. An X-ray structure determination on [Pt₂(μ-S)₂(PPh₃)₄Bi(S₂CNEt₂)₂]PF₆ reveals the presence of a six-coordinated bismuth centre with an approximately nido-pentagonal bipyramidal coordination geometry. Fragmentation pathways for both complexes have been probed using electrospray ionisation mass spectrometry; ions [Pt₂(μ-S)₂(PPh₃)₂Bi(S₂CXEt_n)₂]⁺ (X = O, n = 1, X = N, n = 2) are formed by selective loss of two PPh₃ ligands, and at higher cone voltages the species [(Ph₃P)PtS₂Bi]⁺ is observed. Ions formed by loss of CS₂ are also observed for the xanthate but not the dithiocarbamate ions.     

Synthesis and characterisation of adducts of [Pt2(μ-S)2(PPh3)4] with organo-palladium and platinum-hydride substrates

The reactions of [Pt₂(μ-S)₂(PPh₃)₄] towards a range of palladium(II) complexes containing organometallic ligands (cyclopalladated N-donor ligands, η³-allyl, phenyl) have been explored, leading to the formation of a series of cationic, trinuclear sulfido-bridged aggregates containing {Pt₂PdS₂} cores. [Pt₂(μ-S)₂(PPh₃)₄] also reacts with the platinum(II) hydride complex trans-[PtHCl(PPh₃)₂] giving the adduct [Pt₂(μ-S)₂(PPh₃)₄PtH(PPh₃)]⁺. X-ray crystal structure determinations on the complexes [Pt₂(μ-S)₂(PPh₃)₄PdPh(PPh₃)]PF₆ and [Pt₂(μ-S)₂(PPh₃)₄PtH(PPh₃)]PF₆ are reported, and show the expected bis μ₃-sulfido aggregates with three square-planar metal centres.     

Dinuclear platinum complexes with designer thiolate ligands from the monoalkylation of [Pt2(μ-S)2(PPh3)4]

Alkylation reactions of the nucleophilic platinum(II) sulfide complex [Pt₂(μ-S)₂(PPh₃)₄] with functionalised alkylating agents have been investigated as a versatile synthetic route to dinuclear, cationic sulfide-thiolate complexes of the type [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺, extending the range of thiolate complexes that can be prepared using this methodology. A wide range of functional groups can be incorporated, using appropriate alkylating agents, and include ketone, ester, amide, hydrazone, semicarbazone, thiosemicarbazone, oxime, guanidine, urea and thiourea groups.     

N-Heterocyclic carbene gold(I) and silver(I) adducts of [Pt2(μ-S)2(PPh3)4]

Reaction of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] with the N-heterocyclic carbene (NHC) complexes IPrAuCl, IMesAuCl and IMesAgCl in methanol gave the first examples of metal adducts of [Pt₂(μ-S)₂(PPh₃)₄] that contain NHC ligands, namely [Pt₂(μ-S)₂(PPh₃)₄AuL]⁺ (L = IPr, IMes) and [Pt₂(μ-S)₂(PPh₃)₄AgIMes]⁺. The complexes were isolated as hexafluorophosphate salts. Reaction of [Pt₂(μ-S)₂(PPh₃)₄] with excess IPrAuCl in refluxing methanol yielded only the mono-adduct, in contrast to the behaviour with the gold(I) phosphine complex Ph₃PAuCl, which undergoes double addition giving [Pt₂(μ-SAuPPh₃)₂(PPh₃)₄]²⁺. The X-ray structure of [Pt₂(μ-S)₂(PPh₃)₄AuIPr]PF₆ was determined and reveals that the ‘free’ sulfide is substantially sterically protected by the IPr ligand, accounting for the low reactivity towards addition of a second AgIPr⁺ moiety.     

The reactivity of [Pt2(μ-S)2(PPh3)4] towards difunctional chloroacetamide alkylating agents: Formation of cyclized or bridged products

The reactions of [Pt₂(μ-S)₂(PPh₃)₄] towards some bis(chloroacetamide) alkylating agents have been investigated. Reaction with one mole equivalent of the hydrazine-derived compound ClCH₂C(O)NHNHC(O)CH₂Cl led to the cyclized product [Pt₂{SCH₂C(O)NHNHC(O)CH₂S}(PPh₃)₄]²⁺ which showed two different PPh₃ environments in the ³¹P{¹H} NMR spectrum, as a result of non-fluxional behavior of the dithiolate ligand in solution. Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with the ortho and para isomers of the phenylenediamine-derived bis(chloroacetamides) ClCH₂C(O)NHC₆H₄NHC(O)CH₂Cl gave tetrametallic complexes containing two {Pt₂S₂} moieties spanned by the CH₂C(O)NHC₆H₄NHC(O)CH₂ group. Both the ortho and para isomers were crystallographically characterized; in the ortho isomer there is intramolecular CO···H-N and S···H-N hydrogen bonding involving the two amide groups.     

Sulfide-bridged aggregates from the metalloligand [Pt2(μ-S)2(PPh3)4] and β-diketonate complexes of cobalt(II) and zinc(II)

Reaction of [Pt₂(μ-S)₂(PPh₃)₄] with a range of zinc(II) and cobalt(II) complexes ML₂, where L is a β-diketonate ligand CH₃COCHCOCH₃, PhCOCHCOPh, CF₃COCHCOTh (Th = 2-thienyl)] permits the synthesis of adducts [Pt₂(μ-S)₂(PPh₃)₄M(diketonate)]⁺, isolated as their salts in moderate yields. The cobalt and zinc acetylacetonate complexes were characterised by single-crystal X-ray diffraction studies, which reveal isomorphous structures, with tetrahedral heterometal centres.     

Extending the coordination chemistry of cobalt with the metalloligand [Pt2(μ-S)2(PPh3)4]: Synthesis of the first cobalt(III) derivatives

The coordination chemistry of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] towards cobalt(II) and cobalt(III) centres has been explored using an electrospray ionisation mass spectrometry (ESI MS)-directed methodology. Reaction of [Pt₂(μ-S)₂(PPh₃)₄] with CoCl₂·6H₂O in methanol gave a green-yellow suspension of the known adduct [Pt₂(μ-S)₂(PPh₃)₄CoCl₂], and the CoBr₂ adduct could be similarly prepared. When in situ-generated [Pt₂(μ-S)₂(PPh₃)₄CoCl₂] is reacted with 8-hydroxyquinoline (HQ) and base, the initial product is the cobalt(II) adduct [Pt₂(μ-S)₂(PPh₃)₄CoQ]⁺, which is then converted in air to the cobalt(III) adduct [Pt₂(μ-S)₂(PPh₃)₄CoQ₂]⁺, isolated as its hexafluorophosphate salt. The corresponding picolinate (Pic) derivative [Pt₂(μ-S)₂(PPh₃)₄Co(Pic)₂]⁺ was similarly prepared, however reaction of [Pt₂(μ-S)₂(PPh₃)₄], CoCl₂·6H₂O and 8-(tosylamino)quinoline (HTQ) produced only the cobalt(II) adduct [Pt₂(μ-S)₂(PPh₃)₄CoTQ]⁺. Reactions of [Pt₂(μ-S)₂(PPh₃)₄], CoCl₂·6H₂O and dithiocarbamates gave cobalt(III) complexes [Pt₂(μ-S)₂(PPh₃)₄Co(S₂CNR₂)₂]⁺ [R = Et or R₂ = (CH₂)₄], and proceeded much more rapidly, consistent with the known ability of the dithiocarbamate ligand to stabilize cobalt in higher oxidation states. A study of the fragmentation of cobalt(III) adducts by positive-ion ESI mass spectrometry indicated that [Pt₂(μ-S)₂(PPh₃)₄CoQ₂]⁺ fragments to form the radical cation [Pt₂(μ-S)₂(PPh₃)₄]⁺, which could also be generated by ESI MS analysis of [Pt₂(μ-S)₂(PPh₃)₄] in methanol-NaOH solution. In contrast, the corresponding indium(III) derivative [Pt₂(μ-S)₂(PPh₃)₄InQ₂]⁺, and the cobalt(III) dithiocarbamate [Pt₂(μ-S)₂(PPh₃)₄Co(S₂CN(CH₂)₄)₂]⁺ are much more reluctant to fragment under analogous conditions, and the differences are discussed in terms of cobalt(III) redox chemistry.     

Dithiolate and diselenolate complexes [Pt2(μ-ECH2CHCHCH2E)(PPh3)4] (E = S, Se): Synthesis, characterisation and mass spectrometric formation of the dichalcogenide species [Pt2(μ-E2)(PPh3)4]

The reactions of [Pt₂(μ-E)₂(PPh₃)₄] (E = S, Se) with cis-1,4-dichlorobut-2-ene (cis-ClCH₂CHCHCH₂Cl) give the dichalcogenolate complexes [Pt₂(μ-ECH₂CHCHCH₂E)(PPh₃)₄]²⁺; an X-ray structure determination on the thiolate complex was carried out. The complexes give the expected dications in ESI mass spectra recorded at very low cone voltages, but at moderate cone voltages undergo facile fragmentation via a retro-Diels-Alder reaction and loss of 1,3-butadiene, giving the dichalcogenide species [Pt₂(μ-E₂)(PPh₃)₄]²⁺. Analogous species containing bidentate phosphine or arsine ligands have been previously generated electrochemically, and studied theoretically.     

Synthesis of some pentanuclear platinum clusters [Pt5(CO)6(L)4]. The X-ray structure of [Pt5(μ-CO)5(CO)(PCy3)4]

[Pt₅(μ-CO)₅(CO)L₄] (L = PPh₃1, PPh₂Bz 2, AsPh₃3, PEt₃4, PCy₃5) have been synthesized by reacting [Pt₃(μ-CO)₃(PR₃)₃] with H₂O₂ (1 and 2), by reduction of cis-[PtCl₂(CO)(PEt₃)] with Zn dust (4), and by the Zn reduction of [Pt₃(μ-CO)₃(PCy₃)₃] in the presence of [PtCl₂(CH₃CN)₂] (5). Complex 5 has not been observed previously and has been characterized by X-ray crystallography. Oxidation of the phosphine ligands with H₂O₂ is a new way to synthesize 1 and 2. The first complete NMR characterization of these complexes has also been achieved, and showed that these pentanuclear cluster complexes exhibit similar stereochemistries in solution and in the solid state. The observed ¹J_Pt-Pt values do not have any correlation with the corresponding bond lengths, again pointing out the irregular behaviour of such parameter in Pt complexes.     

Reactivity of [PdCl(μ-med)]2 with monodentate or bidentate ligands. Structure of the dinuclear complexes [Pd(μ-med)(PPh3)]2(BF4)2 and [Pd(μ-med)(bpy)]2(BF4)2. [Hmed=N-(2-mercaptoethyl)-3,5-dimethylpyrazole]

Treatment of the ligand N-(2-mercaptoethyl)-3,5-dimethylpyrazole with [Pd(CH₃COO)₂]₃ and reaction of [PdCl(μ-med)]₂ with pyridine (py) or triphenylphosphine (PPh₃) in the presence of AgBF₄ produced the following complexes: [Pd(CH₃COO)(μ-med)]₂, [Pd(μ-med)(py)]₂(BF₄)₂ and [Pd(μ-med)(PPh₃)]₂(BF₄)₂. Similar reactions carried out with 2,2^′-bipyridine (bpy) or 1,3-bis(diphenylphosphino)propane (dppp) produced [Pd(μ-med)(bpy)]_x(BF₄)_x (x=1 or 2) and [Pd(μ-med)(dppp)]_x(BF₄)_x (x=1 or 2). Treatment of [Pd(μ-med)(bpy)]_x(BF₄)_x with [PdCl₂(CH₃CN)₂] produced [Pd₃Cl₂(μ-med)₂(bpy)₂](BF₄)₂. Treatment of [Pd(μ-med)(dppp)]_x(BF₄)_x with [PdCl₂(CH₃CN)₂] produced a mixture of [Pd(μ-Cl)(dppp)]₂(BF₄)₂ and [Pd(μ-med)₂(dppp)]²⁺. X-ray crystal structures of [Pd(μ-med)(PPh₃)]₂(BF₄)₂ · 2CH₃CN and [Pd(μ-med)(bpy)]₂(BF₄)₂ · 0.5CH₃OH are presented.     

Further studies on the dialkylation chemistry of [Pt2(μ-S)2(PPh3)4] with activated alkyl halides RC(O)CH2X (X = Cl, Br)

Further studies have been carried out into the reactivity of [Pt₂(μ-S)₂(PPh₃)₄] towards a range of activated alkylating agents of the type RC(O)CH₂X (R = organic moiety, e.g. phenyl, pyrenyl; X = Cl, Br). Alkylation of both sulfide centers is observed for PhC(O)CH₂Br, 3-(bromoacetyl)coumarin [CouC(O)CH₂Br], and 1-(bromoacetyl)pyrene [PyrC(O)CH₂Br], giving dications [Pt₂{μ-SCH₂C(O)R}₂(PPh₃)₄]²⁺, isolated as their PF₆⁻ salts. The X-ray structure of [Pt₂{μ-SCH₂C(O)Ph}₂(PPh₃)₄](PF₆)₂ shows the presence of short Pt?O contacts. In contrast, the corresponding chloro compounds [typified by PhC(O)CH₂Cl] and imino analogues [e.g. PhC(NOH)CH₂Br] do not dialkylate [Pt₂(μ-S)₂(PPh₃)₄]. The ability of PhC(O)CH₂Br to dialkylate [Pt₂(μ-S)₂(PPh₃)₄] allows the synthesis of new mixed-alkyl dithiolate derivatives of the type [Pt₂{μ-SCH₂C(O)Ph}(μ-SR)(PPh₃)₄]²⁺ (R = Et or n-Bu), through alkylation of in situ-generated monoalkylated compounds [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ (from [Pt₂(μ-S)₂(PPh₃)₄] and excess RBr). In these heterodialkylated systems ligand replacement of PPh₃ occurs by the bromide ions in the reaction mixture forming monocations [Pt₂{μ-SCH₂C(O)Ph}(μ-SR)(PPh₃)₃Br]⁺. This ligand substitution can be easily suppressed by addition of PPh₃ to the reaction mixture. The complex [Pt₂{μ-SCH₂C(O)Ph}(μ-SBu)(PPh₃)₄]²⁺ was crystallographically characterized. X-ray crystal structures of the bromide-containing complexes [Pt₂{μ-SCH₂C(O)Ph}(μ-SR)(PPh₃)₃Br]⁺ (R = Et, Bu) are also reported. In both structures the coordinated bromide is trans to the SCH₂C(O)Ph ligand, which adopts an axial position, while the ethyl and butyl substituents adopt equatorial positions, in contrast to the structures of the dialkylated complexes [Pt₂{μ-SCH₂C(O)Ph}₂(PPh₃)₄]²⁺ and [Pt₂{μ-SCH₂C(O)Ph}(μ-SBu)(PPh₃)₄]²⁺ (and many other known analogues) where both alkyl groups adopt axial positions.     

Thiolato-bridged “Linear” trinuclear platinum complexes [Pt3(μ-SR)4(dppm)2]

Thiolato-bridged tri- and dinuclear platinum complexes of the types [Pt₃(μ-SR)₄(dppm)₂]²⁺ (1) and [Pt₂(μ-ER)₂(dppm)₂]²⁺ (2) (E=S or Se; R=alkyl or aryl; dppm=bis(diphenylphosphino)methane) have been prepared using the mononuclear precursors [Pt(ER)₂(dppm)]. The complexes have been characterized by NMR (¹H, ¹³C, ³¹P, ¹⁹⁵Pt), FT-IR and FAB mass spectral data. The structure of [Pt₃(μ-SC₆H₄CH₃-4)₄(dppm)₂][CF₃SO₃]₂ · 6CH₂Cl₂ (1d), has been established through X-ray crystallography, revealing a zig-zag arrangement of the three coordination spheres around the platinum atoms.     

Influence of chain length on mono- versus di-alkylation in the reactivity of [Pt2(μ-S)2(PPh3)4] towards α,ω-dihalo-n-alkanes; a synthetic route to platinum(II) ω-haloalkylthiolate complexes

The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with α,ω-dibromoalkanes Br(CH₂)_nBr (n = 4, 5, 6, 8, 12) gave mono-alkylated [Pt₂(μ-S){μ-S(CH₂)_nBr}(PPh₃)₄]⁺ and/or di-alkylated [Pt₂(μ-S(CH₂)_nS}(PPh₃)₄]²⁺ products, depending on the alkyl chain length and the reaction conditions. With longer chains (n = 8, 12), intramolecular di-alkylation does not proceed in refluxing methanol, with the mono-alkylated products [Pt₂(μ-S){μ-S(CH₂)_nBr}(PPh₃)₄]⁺ being the dominant products when excess alkylating agent is used. The bridged complex [{Pt₂(μ-S)₂(PPh₃)₄}₂{μ-(CH₂)₁₂}]²⁺ was accessible from the reaction of [Pt₂(μ-S)₂(PPh₃)₄] with 0.5 mol equivalents of Br(CH₂)₁₂Br. [Pt₂(μ-S){μ-S(CH₂)₄Br}(PPh₃)₄]⁺ can be cleanly isolated as its BPh₄⁻ salt, but undergoes facile intramolecular di-alkylation at −18 °C, giving the known species [Pt₂(μ-S(CH₂)₄S}(PPh₃)₄]²⁺. The reaction of I(CH₂)₆I with [Pt₂(μ-S)₂(PPh₃)₄] similarly gives [Pt₂(μ-S){μ-S(CH₂)₆I}(PPh₃)₄]⁺, which is fairly stable towards intramolecular di-alkylation once isolated. These reactions provide a facile route to ω-haloalkylthiolate complexes which are poorly defined in the literature. X-ray crystal structures of [Pt₂(μ-S){μ-S(CH₂)₅Br}(PPh₃)₄]BPh₄ and [Pt₂(μ-S(CH₂)₅S}(PPh₃)₄](BPh₄)₂ are reported, together with a study of these complexes by electrospray ionisation mass spectrometry. All complexes fragment by dissociation of PPh₃ ligands, and the bromoalkylthiolate complexes show additional fragment ions [Pt₂(μ-S){μ-S(CH₂)_n−2CHCH₂}(PPh₃)_m]⁺ (m = 2 or 3; m ≠ 4), most significant for n = 4, formed by elimination of HBr.     

Reaction of [Pt3(μ-CO)3(PBu3)3] with activated olefins and alkynes: the X-ray-structure of [Pt(CO)(PBu3)(CF3CCCF3)]

The reactions of the triangulo-cluster [Pt₃(μ-CO)₃(P^tBu₃)₃] with activated olefins and alkynes have been examined under various conditions. At low temperature, cluster fragmentation occurs yielding the Pt(0) complexes [Pt(CO)(P^tBu₃)(olefin)] (olefin = maleic anhydride and maleimide), while di(tert-butyl)acetylenedicarboxilate reacts quantitatively giving the dinuclear Pt(0) complex [Pt₂(CO)₂(P^tBu₃)₂(μ-η²:η²-^tBuO₂CCCCO₂^tBu)]. At higher temperature and in the presence of alkyne in large excess, the latter dimer converts quantitatively to the monomers [Pt(CO)(P^tBu₃)(alkyne)] (alkyne = CF₃CCCF₃ and ^tBuO₂CCCCO₂^tBu). The stereochemistry of these complexes has been established by NMR and IR measurements. The structure of [Pt(CO)(P^tBu₃)(CF₃CCCF₃)] was confirmed by X-ray diffraction analysis.     

Synthesis and structural characterisation of the lead-platinum sulfido aggregates [Pt2(μ-S)2(PPh3)4PbX2] (X = Br, I); promotion of rare tetrahedral geometry for lead(II)

The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with excess PbBr₂ or PbI₂ in methanolic suspension result in the formation of the neutral lead(II) halide adducts [Pt₂(μ-S)₂(PPh₃)₄PbX₂] (X = Br, I). The X-ray structure determination of the lead iodide adduct reveals an essentially tetrahedral lead(II) centre, which is a rare coordination geometry for lead(II), which almost invariably is hemidirected, with a stereochemically active lone pair. In contrast, the structure of the PbBr₂ adduct, although suffering from some disorder, shows a more typical, distorted arrangement of ligands; these results are discussed in terms of the tendency for soft, bulky ligands to promote symmetric, holodirected geometries. The ESI mass spectra of the adducts are reported, and yield [M−halide]⁺ ions.     

An electrospray mass spectrometry-directed survey of the coordination chemistry of the metalloligand [Pt2(μ-S)2(PPh3)4] with platinum(II) and palladium(II) chloride substrates: influence of metal-ligand lability on product type

The reactivity of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] towards a wide range of platinum(II) and palladium(II) chloride complex substrates [L₂MCl₂] has been explored, using the technique of electrospray ionisation mass spectrometry to directly analyse reaction solutions. In the majority of cases, products are formed by addition of the ML₂²⁺ fragment to the {Pt₂S₂} core, giving trinuclear species [Pt₂(μ-S)₂(PPh₃)₄ML₂]²⁺. The adducts with Pt(diene) [diene=cyclo-octa-1,5-diene (cod), norbornadiene], Pd(cod), Pd(bipy) (bipy=2,2^′-bipyridine), Pt(PMe₃)₂ and Pt(PTA)₂ (PTA=phosphatriaza-adamantane) moieties were synthesised and characterised on the macroscopic scale, with [Pt₂(μ-S)₂(PPh₃)₄Pt(cod)] (BF₄)₂ and [Pt₂(μ-S)₂(PPh₃)₄Pd(bipy)] (PF₆)₂ also characterised by X-ray diffraction studies. No metal scrambling was found to occur, as has been observed in some previous cases involving the related complexes [Pt₂(μ-Se)₂(PPh₃)₄] and [Pt₂(μ-S)₂(dppe)₂] (dppe=Ph₂PCH₂CH₂PPh₂). With cis-[PtCl₂(SOMe₂)₂] the species [Pt₂(μ-S)₂(PPh₃)₄PtCl(SOMe₂)]⁺ was formed, as a result of the lability of the SOMe₂ ligand. With palladium(II)-phosphine systems, the observed product species is dependent on the phosphine; the bulky PPh₃ ligand in [PdCl₂(PPh₃)₂] leads primarily to the analogous known species [Pt₂(μ-S)₂(PPh₃)₄PdCl(PPh₃)]⁺, and a small amount of the metal-scrambled species [PtPd₂S₂(PPh₃)₅Cl]⁺. In contrast, [PdCl₂(PTA)₂], containing the small PTA ligand gave [Pt₂(μ-S)₂(PPh₃)₄Pd(PTA)₂]²⁺.     

Thiotungstates containing the syn-[W2(O/S)2(μ-S)2] (E = O, S) and cuboidal [W2Cu2(μ3-S)4] cores

Reaction of [W^VIS₄]²⁻ with ethane-1,2-dithiol edtH₂ in the presence of the sulfide scavenger Cd²⁺ yielded the dinuclear tungstate syn-[{(edt)W^V(O/S)}₂(μ-S)₂]²⁻ (1), with the terminal S/O disordered over the two tungsten sites in the ratio 0.8:02. In the presence of thiocyanate, phosphine and CuI, the anionic cuboidal clusters of composition [{(SCN)₃W^V}₂{Cu^I(PPh₃)}₂(μ₃-S)₄]²⁻ (2) and (3, diphos = 1,2-bis(o-diphenylphosphinophenyl)ethane), and possibly via an intermediate [{(SCN)₃W^VS}₂(μ-S)₂]⁴⁻. The crystal and molecular structures of [Et₄N]₂1, [Et₄N]₂2 · H₂O and [Et₄N]₂3 · H₂O have been determined.     

Chalcogenide-capped triruthenium clusters: X-ray structures of [Ru3(CO)6(μ3-CO){P(C4H3S)3}(μ-dppm)(μ3-O)] and [(μ-H)2Ru3(CO)6{P(C4H3S)3}(μ-dppm)(μ3-S)]

Treatment of [Ru₃(CO)₉{P(C₄H₃S)₃}(μ-dppm)] (1) [dppm = bis(diphenylphosphino)methane] with molecular oxygen in benzene at 60 °C affords oxo-capped [Ru₃(CO)₆(μ₃-CO){P(C₄H₃S)₃}(μ-dppm)(μ₃-O)] (2), while with elemental sulfur and selenium related chalcogenide-capped clusters [Ru₃(CO)₆(μ₃-CO){P(C₄H₃S)₃}(μ-dppm)(μ₃-E)] (3, E = S; 5, E = Se) and bis(chalcogenide) clusters [Ru₃(CO)₆{P(C₄H₃S)₃}(μ-dppm)(μ₃-E)₂] (4, E = S; 6, E = Se) result. Reaction of 1 with H₂S in refluxing THF affords the previously reported [(μ-H)₂Ru₃(CO)₇(μ-dppm)(μ₃-S)] (7) together with the new sulfido-capped dihydride [(μ-H)₂Ru₃(CO)₆{P(C₄H₃S)₃}(μ-dppm)(μ₃-S)] (8). All new compounds have been characterized by spectroscopic data, and 2 and 8 by single-crystal X-ray diffraction analyses. Oxo-capped 2 consists of a triangular ruthenium framework capped on opposite sides by oxo and carbonyl groups, while 8 consists of a ruthenium triangle by a capping sulfido ligand and two inequivalent bridging hydride ligands.