Sulfido Clusters Research Articles

Incorporation of Three Phenylacetylene Molecules into an RhMo2S4 Trinuclear Sulfido Cluster Core, Forming Bridging Metallathiacyclobutene and Dithiolene Moieties

The trinuclear sulfido cluster [{Rh(PPh3)2}(μ3-S)(μ2-S)3{Mo(S2CNEt2)}2(μ2-Cl)] (2a) reacted readily with three PhC⋮CH molecules to afford [{Rh(SCPhCH)Cl(PPh3)}{Mo(SCPhCH)(S2CNEt2)}{Mo(S2C2HPh)(S2CNEt2)}], the structure of which, as well as that of the PMePh2 analogue of 2a, have been determined by X-ray analyses.

A Ti(2)Ru(2)Pd(2) oxo-sulfido cluster synthesized by linking two rationally preorganized TiRuPdS(2) heterotrimetallic units with an oxo ligand: its reaction with an alkyne.

A Ti(2)Ru(2)Pd(2) oxo-sulfido cluster synthesized by linking two rationally preorganized TiRuPdS(2) heterotrimetallic units with an oxo ligand: its reaction with an alkyne.

Methylcyclopentadienyl-substituted tungsten(IV) sulfido cluster [(eta5-Cp')3W3S4]+ and its heterobimetallic derivative [(eta5-Cp')3W3S4Ni(PPh3)]+ .

The aqueous cluster salt [(H2O)9W3S4][pts]4.9H2O (pts = p-toluenesulfonate) was converted to the methylcyclopentadienyl (Cp') substituted cluster [(eta5-Cp')3W3S4][pts] ([1][pts]) from which the cubane-like cluster [(eta5-Cp')3W3S4Ni(PPh3)][pts] ([2][pts]) was obtained by reaction with Ni(cod)2 and PPh3. [2][pts] was characterized by X-ray crystal structure analysis.

Synthesis and structures of heterobimetallic Ir 2M (MPd, Pt) sulfido clusters and their catalytic activity for regioselective addition of alcohols to internal 1-aryl-1-alkynes

The heterobimetallic trinuclear sulfido clusters [(Cp*Ir) 2(μ 3-S) 2MCl 2] (M=Pd ( 3), Pt ( 4); Cp*=η 5-C 5Me 5) were synthesized from the dinuclear hydrogensulfido complex [Cp*IrCl(μ-SH) 2IrCp*Cl] ( 2) and [MCl 2(COD)] (COD=cycloocta-1,5-diene), while the reaction of 2 with [Pd(PPh 3) 4] afforded the cationic trinuclear cluster [(Cp*Ir) 2(μ 3-S) 2PdCl(PPh 3)]Cl ( 5). Clusters 3 and 4 reacted with PPh 3 to give a series of mono and dicationic clusters including 5, while the dicationic clusters [(Cp*Ir) 2(μ 3-S) 2M(dppe)][BPh 4] 2 (M=Pd ( 9), Pt ( 10); dppe=Ph 2PCH 2CH 2PPh 2) were obtained by the reaction with dppe followed by anion metathesis. The molecular structures of 5·CH 2Cl 2, 9·CH 3COCH 3, and 10·CH 3COCH 3 were determined by X-ray crystallography. Clusters 3 and 4 were found to catalyze the addition of alcohols to alkynes to give the corresponding acetals. Internal 1-aryl-1-alkynes were transformed by cluster 3 into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity up to 99:1, while cluster 4 was a much less regioselective catalyst.

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Proton reactivity of butterfly oxo and sulfido clusters and structural characterization of HFe3Mn(CO)10(dmpm)(μ4-O)

Phosphine substitution for CO in the butterfly oxo cluster [Fe3Mn(CO)12(μ4-O)]− (1) produces the bis-phosphine clusters [Fe3Mn(CO)10(PR3)2(μ4-O)]− (R=OCH3 (2a), CH3 (2b)) and [Fe3Mn(CO)10(dmpm)(μ4-O)]− (3). In the presence of the strong acid, HSO3CF3, the oxo cluster 1 is not protonated, 3 is protonated at the Fe-Fe backbone of the butterfly, and [Fe3Mn(CO)12(μ4-S)]− (5) loses CO and Mn upon protonation to yield H2Fe3(CO)9(μ3-S) and a manganese containing by-product. The structure of the protonated cluster HFe3Mn(CO)10(dmpm)(μ4-O) (4), determined by single-crystal X-ray diffraction, compared with its parent, 1, compound 4, has elongated metal-metal bonds, a smaller dihedral angle (111° compared to 113°), and shorter wingtip metal-to-oxo ligand distances. Additionally, the carbonyl ligands on 4 shift to accommodate the hydride ligand on the hinge iron metals and the bidentate phosphine ligand spanning the hinge and wingtip iron atoms. The butterfly clusters were characterized by 1H NMR, variable temperature 13C NMR, 31P NMR, and infrared spectroscopy. Crystal data for 4: monoclinic (Cc), a=7.917(2), b=18.541(2), c=16.196(1) Å, β=95.41(1)°, Z=4, R (Rw)=0.022 (0.029).

Synthesis and Characterization of Mixed-Metal Sulfido Clusters with the Cubane-Type PtMo3S4 Core

Abstract The reaction of the incomplete cubane-type cluster [Mo3(μ3-S)(μ-S)3(H2O)9]Cl4 (1) and [Pt(dba)2] (dba = 1,5-diphenyl-1,4-pentadien-3-one) in MeOH gave a brown precipitate (4) that contains platinum and molybdenum in the atomic ratio of 1 : 3. Further treatment of 4 with 3 equiv of dppe (dppe = 1,2-bis(diphenylphosphino)ethane) gave the cubane-type cluster [PtMo3(μ3-S)4Cl4(dppe)3] (5) in 37% yield, whose molecular structure was unambiguously characterized by X-ray diffraction study of 5·2CH2ClCH2Cl·2H2O. A similar reaction of 4 with 4 equiv of dppe afforded the cationic cluster [PtMo3(μ3-S)4Cl3(dppe)4]Cl (6) in 29% yield, which was characterized spectroscopically. The Pd-Mo and Ni-Mo analogues of the above Pt-Mo clusters, [PdMo3(μ3-S)4Cl3(dppe)4]Cl·CH2Cl2 (7) and [NiMo3(μ3-S)4Cl4(dppe)3] (8), were also synthesized by the reactions of the corresponding aqua clusters with dppe.

Preparation and crystal structures of formato complexes of the [MIV3O4]4+ and [MIV3S4]4+ (M = Mo, W) clusters. Convenient precursors to the corresponding aqua complexes.

In the aqueous chemistry of molybdenum(IV) and tungsten(IV), trinuclear, incomplete cubane-like, oxo and sulfido clusters of the type [M3E4]4+ (M = Mo, W; E = O, S) play a central role. We here describe how formato complexes of all these cluster cores can be prepared in high yields by crystallization from methanol-water or ethanol-water mixtures. Since potassium and ammonium formate are very soluble in these alcohol-water mixtures, high formate concentrations could be accomplished in the solutions from which the corresponding salts of cluster formato complexes crystallized. The [Mo3O4]4+ compounds could be synthesized without requiring the use of noncomplexing acids in the process. Some [M3E4]4+ compounds were characterized by single-crystal structure determinations. [NH4]3.20[K]0.80[H3O][Mo3O4(HCO2)8][HCO2].H2O was triclinic, space group P1 (No. 2) with a = 11.011(2) A, b = 13.310(2) A, c = 9.993(1) A, alpha = 106.817(7) degrees, beta = 91.651(9) degrees, gamma = 88.340(9) degrees, and two formula units per cell. [K]6[W3S4(HCO2)9][HCO2].2.27H2O.0.73CH3OH was monoclinic, space group C2/m (No. 12) with a = 19.605(6) A, b = 14.458(7) A, c = 13.627(5) A, beta = 118.94(2) degrees, and four formula units per cell. Generally, the nine coordination sites of [M3E4]4+ were occupied either by a mixture of monodentate and mu 2-bridging formato ligands or by monodentate formato ligands only. By dissolution in noncomplexing strong acid, all the formato complexes immediately hydrolyzed to form [M3E4(H2O)9]4+ aqua complexes. This allows, for example, high concentrations of [Mo3S4(H2O)9]4+ in CF3SO3H to be obtained and these solutions to be used for the synthesis of bimetallic clusters containing the cubane-like motif Mo3M'S4.

Acid and base assisted topological reorganization of gallium sulfido clusters

The reaction of [(tBu)Ga(μ3-S)]4 with nPrNH2 in toluene solution yields [(tBu)6Ga6(μ3-S)4(μ-S)2(NH2nPr)2] (1), whose thermolysis in the solid state (110 °C), results in the stoichiometric conversion to [(tBu)Ga(μ3-S)]6 (ΔH‡ = 136 kJ mol−1); in contrast, the reaction of [(tBu)Ga(μ3-S)]4 with triflic acid at room temperature yields [(tBu)Ga(μ3-S)]7.

Synthesis and reactivities of cubane-type sulfido clusters containing noble metals.

Cubane-type sulfido clusters containing noble metals are newcomers compared with the corresponding clusters of the first transition series metals and molybdenum, which have been extensively studied in relation to metalloenzymes and industrial hydrodesulfurization catalysts. This Account reviews the recent progress in studies on the synthesis and reactivities of these noble metal cubane-type clusters. One of the goals in this new area lies in development of the unique catalysis of the noble metals embedded in the robust and redox-active cubane-type cores. Rational synthetic approaches indispensable to the preparation of such effective cluster catalysts are discussed to a significant extent.

Synthesis, crystal structure and nonlinear optical properties of two new cluster compounds: [WCu 3S 4(PPh 3) 3{S 2P(OCH 2Ph) 2}] and [WAg 3OS 3(Ph 3P) 3{S 2P(OPr i) 2}

Two new O, O′-dialkyl dithiophosphate-containing sulfido clusters, [WCu 3S 4(PPh 3) 3{S 2P(OCH 2Ph) 2}] 1 and [WAg 3OS 3(Ph 3P) 3{S 2P(OPr i) 2}] 2, were synthesized through reactions of [NH 4] 2[WS 4] with [CuS 2P(OCH 2Ph) 2] and [NH 4] 2[WOS 3] with [AgS 2P(OPr i) 2], respectively. Their crystal structures and nonlinear optical properties are reported. The X-ray crystallographic structure of 1 is an incomplete cubane-like structure, the dithiophosphate ligand adopts a triply bridging role, employing two sulfur atoms to coordinate to the three Cu atoms: one sulfur atom binds to one Cu atom, another sulfur atom to two other Cu atoms. The structure of 2 contains a half-open cubane-like cluster core, the dithiophosphate ligand acts as a bidentate ligand and the two S atoms of the di-isopropyl dithiophosphato ligand coordinate to two Ag atoms, respectively. Using a Z-scan technique with 532 nm laser radiation, both the real and imaginary parts of third-order nonlinear susceptibility of clusters 1 and 2 were determined.

(THF)(8)Ln(8)E(6)(EPh)(12) Cluster Reactivity: Systematic Control of Ln, E, EPh, and Neutral Donor Ligands.

Octametallic (L)(8)Ln(8)E(6)(EPh)(12) clusters (L = Lewis base; Ln = lanthanide ion; E = S, Se; EPh = SPh, SePh) can be prepared either by the reduction of Se-C bonds with low-valent Ln or by the reaction of Ln(SePh)(3) with elemental E. Because all possible ligand sites (i.e., L, E, EPh) are reactive, the ligands can be varied systematically to further the understanding of structure/property relationships. Chalcogenolate ligands can be selectively varied, as in the reaction of (THF)(8)Sm(8)Se(6)(SePh)(12) with PhSSPh to form (THF)(8)Sm(8)Se(6)(SPh)(12). Neutral L can be altered without disrupting structure, as in the replacement of THF with pyridine to give (py)(8)Sm(8)Se(6)(SePh)(12). Even chalcogenido ligands can be chemically replaced: the reaction of (THF)(8)Sm(8)Se(6)(SPh)(12) with elemental S gives the all-sulfur cluster (THF)(8)Sm(8)S(6)(SPh)(12). All compounds were isolated and characterized by IR and UV-visible spectroscopy and by low-temperature single-crystal X-ray diffraction to confirm that the structures contain cubes of Ln(III) ions with E(2)(-) capping the faces and EPh bridging the edges of the cube. The Sm(8)Se(6)(EPh)(12) clusters are intensely colored because of a Se(2)(-) to Sm(III) charge transfer absorption, while the sulfido clusters exhibit the light yellow color characteristic of Sm(III) complexes. The light green Nd complex (py)(8)Nd(8)Se(6)(SePh)(12) was isolated from the reaction of Nd(SePh)(3) with Se to confirm that chalcogenolate displacement is general to the redox-inactive lanthanides and that the intense colors of the Sm selenido clusters are related to the redox activity of the Ln. The two pyridine complexes (py)(8)LnSe(6)(SePh)(12) (Ln = Nd, Sm) are isostructural. Crystal data (Mo Kalpha, 153(2) K) are as follows. (THF)(8)Sm(8)Se(6)(SPh)(12): triclinic space group P&onemacr;, a = 17.637(7) Å, b = 18.337(5) Å, c = 20.466(12) Å, alpha = 103.04(4) degrees, beta = 94.71(4) degrees, gamma = 94.28(3) degrees, Z = 2. (py)(8)Sm(8)Se(6)(SePh)(12): monoclinic space group C2/m, a = 18.770(2) Å, b = 28.113(4) Å, c = 16.461(3) Å, beta = 120.65(1) degrees, Z = 2. (THF)(8)Sm(8)S(6)(SePh)(12): orthorhombic space group Pcab, a = 19.803(3) Å, b = 22.446(3) Å, c = 26.072(4) Å, Z = 8.

Electron-Deficient Early−Late Heterobimetallic Sulfido Clusters. Unusual Reactivities of Ti2Ru2S4 Cubane-Type Clusters with Four Cyclopentadienyl Coligands

Treatment of [Cp2Ti(SH)2] (1; Cp = η5-C5H5) with [(Cp*Ru)4(μ3-Cl)4] (2; Cp* = η5-C5Me5) in a Ti:Ru ratio of 1:1 afforded the hydrosulfido-bridged titanium−ruthenium heterobimetallic complex [Cp2Ti(μ2-SH)2RuClCp*] (3). Complex 3 reacted with an excess of triethylamine to give the early−late heterobimetallic cubane-type sulfido cluster [(CpTi)2(Cp*Ru)2(μ3-S)4] (4), with a loss of HCl and cyclopentadiene. An X-ray diffraction study and extended Hückel molecular orbital calculations for the 60e- cluster 4 demonstrated that 4 has four Ru→Ti dative bonds and a weak Ti−Ti interaction. The reaction of 4 with 3 equiv of [Cp2Fe][PF6] afforded the dicationic cubane-type cluster [(CpTi)2(Cp*Ru)2(μ3-S)4][PF6]2 (5), which contains an additional Ru−Ru bond. In contrast, oxidation of 4 with an excess of HCl at room temperature resulted in the formation of the neutral dichloride cluster [(CpTiCl2)(CpTi)(Cp*Ru)2(μ3-S)4] (6). Clusters 5 and 6 were converted into each other by treatment with chloride or hexafluorophosphate anion. Furthermore, substitution of one of the cyclopentadienyl ligands in 6 by a chloride anion took place in boiling 1,2-dichloroethane to give the trichloride cluster [(TiCl3)(CpTi)(Cp*Ru)2(μ3-S)4] (7). The detailed structures of these oxidized cubane-type clusters 5·2DMF, 6·CH2Cl2, and 7·CH2Cl2 as well as the hydrosulfido-bridged dinuclear complex 3 have also been determined by X-ray crystallography. The Ti2Ru2S4 cubane-type cores in 5−7 differ considerably in structure from each other, depending upon the ancillary ligands bound to the Ti atoms, although they have a Ru−Ru bond and two Ru→Ti dative bonds in common.

Syntheses of mixed-metal M2Ti2S4 cubane-type sulfido clusters (M = Ru, Rh, Ir, Cu) from a dinuclear organometallic thiotitanate anion

The dinuclear organometallic thiotitanate anion [(CpTiS)2(µ-S)2]2– reacted with [Cp*Ru(µ3-Cl)]4, [(cod)M(µ-Cl)]2 (M = Rh, Ir) and [Cu(µ3-Cl)(PPh3)]4 to afford the early–late heterobimetallic cubane-type sulfido clusters [(CpTi)2(Cp*Ru)2(µ3-S)4], [(CpTi)2{M(cod)}2(µ3-S)4] and [(CpTi)2{Cu(PPh3)}2(µ3-S)4], respectively.

Synthesis and reactivities of Ir2Ru heterobimetallic sulfido clusters derived from a hydrogensulfido-bridged diiridium complex

The hydrogensulfido-bridged diiridium complex [ClCp*Ir(µ-SH)2IrCp*Cl] reacted with [RuH2(PPh3)4] to give a mixed-metal trinuclear cluster with an Ir2Ru(µ3-S)2 core [(Cp*Ir)2(µ3-S)2RuCl2(PPh3)] 2, which was further converted into the cationic diphosphine derivatives [(Cp*Ir)2(µ3-S)2RuCl(L)]Cl (L = dppe = Ph2PCH2CH2PPh2 3 or depe = Et2PCH2CH2PEt2 4). The reaction of cluster 3 with Me2CuLi followed by anion metathesis with KPF6 afforded the cationic methyl cluster [(Cp*Ir)2(µ3-S)2RuMe(dppe)][PF6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formation of [(Cp*Ir){(η4-C5Me5CHCl2)Ir}(µ3-S)2RuCl(dppe)] 6, in which one of the Cp* ligands was alkylated by CHCl2Li to form an η4-diene. Clusters 3 and 4 were also transformed into the dihydrido clusters [(Cp*Ir)2(µ3-S)2(µ-H)2Ru(L)] (L = dppe 7 or depe 8) by the reaction with NaBH4. On the other hand, cluster 2 was converted into the carbonyl cluster [(Cp*Ir)2(µ3-S)2RuCl(CO)(PPh3)]Cl 9, the isocyanide clusters [(Cp*Ir)2(µ3-S)2RuCl(CNXy)(PPh3)]Cl 10 (Xy = 2,6-C6H3Me2) and [(Cp*Ir)2(µ3-S)2Ru(CNXy)2(PPh3)][BPh4]2 11 and the co-ordinatively unsaturated thiolato clusters [(Cp*Ir)2(µ3-S)2Ru(SAr)2] (Ar = 2,4,6-C6H2Pri3 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular structures of [(Cp*Ir)2(µ3-S)2RuCl(depe)][BPh4] 4′, 5·CH2Cl2, 6, 7 and 12·2C6H6 were established by X-ray diffraction studies.

Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Incomplete Cubane-Type M2M‘S4and Cubane-Type M2M‘2S4Cores (M = Mo, W; M‘ = Rh, Ir)

The reactions of sulfido-bridged dimolybdenum and ditungsten complexes [M2S2(μ2-S)2(S2CNEt2)2] (1; M = Mo, W) with an equimolar amount of [M‘Cl(PPh3)3] (M‘ = Rh, Ir) gave a series of mixed-metal incomplete cubane-type sulfido clusters [M‘(PPh3)2(μ3-S)(μ2-S)3{M(S2CNEt2)}2(μ2-Cl)]. On the other hand, mixed-metal cubane-type sulfido clusters [{M‘(cod)}2{MCl(S2CNEt2)}2(μ3-S)4] (M‘ = Rh, Ir; cod = 1,5-cyclooctadiene) were obtained by the reactions of 1 with an equimolar amount of [M‘Cl(cod)]2. Detailed structures of [Ir(PPh3)2(μ3-S)(μ2-S)3{W(S2CNEt2)}2(μ2-Cl)]·2CH2Cl2 (3b·2CH2Cl2) and [{Rh(cod)}2{MoCl(S2CNEt2)}2(μ3-S)4]·0.5CH2Cl2 (4a·0.5CH2Cl2) have been determined by X-ray crystallography. Compound 3b·2CH2Cl2 crystallized in the monoclinic system, space group P21/n, with a = 10.521(4) A, b = 32.325(5) A, c = 17.277(3) A, β = 96.34(2)°, and Z = 4. Refinement by full-matrix least-squares techniques gave final residuals R = 0.071 and Rw = 0.068. Compound 4a·0.5CH2Cl2 crystallized in the monoclinic system, space ...

Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Trimetallic M2M‘S4(M = Mo, W; M‘ = Pd, Pt) and Tetrametallic Cubane-Type Mo2Pd2S4Cores

The reaction of the sulfido-bridged dimolybdenum or ditungsten complex [M2S2(μ2-S)2(S2CNEt2)2] (M = Mo (1a), W) with an equimolar amount of [M‘(PPh3)4] (M‘ = Pd, Pt) gave a series of mixed-metal sulfido clusters with a trimetallic M2M‘ core [M‘(PPh3)(μ2-S)2{M(S2CNEt2)}2(μ2-S)2]. The X-ray diffraction study for [Pt(PPh3)(μ2-S)2{W(S2CNEt2)}2(μ2-S)2] (3b) has disclosed the presence of a novel triangular framework, for which the two Pt−W edges are each bridged by one μ2-S ligand and the remaining W−W edge is supported by two μ2-S ligands. Cluster 3b crystallized in the monoclinic system, space group C2/c with a = 13.718(3) A, b = 12.795(2) A, c = 43.798(2) A, β = 95.24(1)°, and Z = 8. Refinement by full-matrix least-squares techniques gave final residuals R = 0.052 and Rw = 0.038. Treatment of [Pd(PPh3)(μ2-S)2{Mo(S2CNEt2)}2(μ2-S)2] with an additional amount of [Pd(PPh3)4] resulted in the formation of the cubane-type mixed-metal sulfido cluster [{Pd(PPh3)}2{Mo(S2CNEt2)}2(μ3-S)4], which was also obtained straig...

Structures and Reactivities of Diruthenium Dithiolene Complexes and Triruthenium Sulfido Clusters Derived from a Hydrosulfido-Bridged Diruthenium Complex.

Structures and Reactivities of Diruthenium Dithiolene Complexes and Triruthenium Sulfido Clusters Derived from a Hydrosulfido-Bridged Diruthenium Complex.

Hydrosulfido-Bridged Titanium-Ruthenium Heterobimetallic Complex: Stepwise Construction of Ti2Ru2S4 Cubane-Type Sulfido Cluster

Abstract Reaction of [Cp2Ti(SH)2] (Cp = η5-C5H5) with [(Cp*Ru)4(μ3-Cl)4] (Cp* = η5 - C5Me5) afforded the hydrosulfido-bridged titanium-ruthenium heterobimetallic complex [Cp2Ti(μ2-SH)2RuClCp*] (3), which was further converted into the heterobimetallic cubane-type sulfido cluster [(CpTi)2(Cp*Ru)2(μ3-S)4] (4) upon treatment with an excess of triethylamine. The structures of 3 and 4 have been determined by X-ray crystallography.

Regioselective Addition of Alcohols to Internal 1-Aryl-1-alkynes Catalyzed by a Triangular Heterobimetallic Ir2Pd Sulfido Cluster

Abstract The triangular heterobimetallic sulfido cluster[(Cp*Ir)2(μ3-S)2PdCl2] prepared from [PdCl2(cod)] and [Cp*IrCl(μ-SH)2IrCp*Cl] was found to catalyze the addition of alcohols to alkynes to give the corresponding ketals. In particular, internal 1-aryl-1-alkynes were transformed into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity. The analogous Ir2PtS2 cluster proved to be much less selective.