Disulfido Ligand Research Articles

Time-Resolved Spectroscopy and High-Efficiency Light-Driven Hydrogen Evolution of a {Mo3 S4 }-Containing Polyoxometalate-Based System.

Polyoxothiometalate ions (ThioPOM) are active hydrogen-evolution reaction (HER) catalysts based on modular assembly built from electrophilic clusters {MoSx } and vacant polyoxotungstates. Herein, the dumbbell-like anion [{(PW11 O39 )Mo3 S4 (H2 O)3 (OH)}2 ]8- exhibits very high light-driven HER activity, while the active cores {Mo3 S4 } do not contain any exposed disulfido ligands, which were suspected to be the origin of the HER activity. Moreover, in the catalyst architecture, the two central {Mo3 S4 } cores are sandwiched by two {PW11 O39 }7- subunits that act as oxidant-resistant protecting groups and behave as electron-collecting units. A detailed photophysical study was carried out confirming the reductive quenching mechanism of the photosensitizer [Ir(ppy)2 (dtbbpy)]+ by the sacrificial donor triethanolamine (TEOA) and highlighting the very high rate constant of the electron transfer from the reduced photosensitizer to the ThioPOM catalyst. Such results provide new insights into the field of molecular catalytic systems able to promote high HER activity.

New examples of μ- η2: η2-disulfido dicopper(II,II) complexes with bis(tetramethylguanidine) ligands

The new ligand N, N′ -(2-methyl-2-(2-pyridyl)propan-1,3-diyl)bis(tetramethylguanidine) (L) and its four-coordinate, distorted square-planar copper(II) complex [CuLCl 2] ( 1) were synthesized and structurally characterized. Similarly, bis( μ-OH)dicopper(II,II) complex [Cu 2L 2(OH) 2](OTf) 2 ( 2) was synthesized and structurally characterized. The pyridyl group in L does not coordinate in either 1 or 2. New examples of μ- η 2: η 2-disulfido dicopper(II,II) complexes were synthesized by treating a copper(I) complex of either L or L′ [L′ = 2′,2′-(propane-1,3-diyl)bis(1,1,3,3-tetramethylguanidine)] with elemental sulfur. [Cu 2L 2(S 2)](PF 6) 2 ( 3) and [Cu 2 L 2 ′ (S 2)](PF 6) 2 ( 4) were both structurally characterized, and both structures have two copper(II) ions bridged by a disulfido ligand in a μ- η 2: η 2-manner. The ligands L and L′ coordinate in a bidentate fashion (like 1 and 2, the pyridyl ring does not coordinate in 3), and the geometry around the copper ions in 3 and 4 is distorted square planar. The metrical parameters of 3 and 4 were found to be similar to other μ- η 2: η 2-disulfido dicopper(II,II) complexes, and the Cu–S and Cu···Cu distances are among the shortest reported for this class of copper disulfide dimers.

Disulfido iron–manganese carbonyl cluster complexes: Synthesis, structure, bonding and properties of the radical CpFeMn 2(CO) 7(μ 3-S 2) 2

Two new compounds CpFeMn 2(CO) 7(μ 3-S 2) 2 ( 2) and Cp 3Fe 3Mn(CO) 4(μ 3-S 2) 2(μ 3-S) ( 3) were obtained by the treatment of [CpFeMn(CO) 5(μ 3-S 2)] 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 FeMn 2 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.

C−H Cleavage and Double Alkyl Additions to the Disulfido Ligand in Dicyanido-Bridged Ru2S2 Complexes

Novel dicyanido-bridged dicationic RuIIISSRuIII complexes [{Ru(P(OCH3)3)2}2(mu-S2)(mu-X)2{mu-m-C6H4(CH2CN)2}](CF3SO3)2 (4, X=Cl, Br) were synthesized by the abstraction of the two terminal halide ions of [{RuX(P(OCH3)3)2}2(mu-S2)(mu-X)2] (1, X=Cl, Br) followed by treatment with m-xylylenedicyanide. 4 reacted with 2,3-dimethylbutadiene to give the C4S2 ring-bridged complex [{Ru(P(OCH3)3)2}2{mu-SCH2C(CH3)=C(CH3)CH2S}(mu-X)2{mu-m-C6H4(CH2CN)2}](CF3SO3)2 (6, X=Cl, Br). In addition, 4 reacted with 1-alkenes in CH3OH to give alkenyl disulfide complexes [{Ru(P(OCH3)3)2}2{mu-SS(CH2C=CHR)}(mu-Cl)2{mu-m-C6H4(CH2CN)2}](CF3SO3) (7: R=CH2CH3, 9: R=CH2CH2CH3) and alkenyl methyl disulfide complexes [{Ru(P(OCH3)3)2}2{mu-S(CH3)S(CH2C=HR)}(mu-Cl)2{mu-m-C6H4(CH2CN)2}](CF3SO3)2 (8: R=CH2CH3, 10: R=CH2CH2CH3) via the activation of an allylic C-H bond followed by the elimination of H+ or condensation with CH3OH. Additionally, the reaction of 4 with 3-penten-1-ol gave [{Ru(P(OCH3)3)2}2{mu-SS(CH2C=CHCH2OH)}(mu-Cl)2{mu-m-C6H4(CH2CN)2}](CF3SO3) (11) via the elimination of H+ and [{Ru(P(OCH3)3)2}2(mu-SCH2CH=CHCH2S)(mu-Cl)2{mu-m-C6H4(CH2CN)2}](CF3SO3)2 (12) via the intramolecular elimination of a H2O molecule. 12 was exclusively obtained from the reaction of 4 with 4-bromo-1-butene.

Disulfido Metal Carbonyl Complexes Containing Manganese

AbstractFor Abstract see ChemInform Abstract in Full Text.

Disulfido Metal Carbonyl Complexes Containing Manganese

An account of recent studies of the chemistry of new disulfido metal carbonyl complexes containing manganese is presented. The coordination of the disulfido ligands, the nature of reactions at the manganese atom(s) and the nature of insertion reactions at the disulfido ligands are discussed.

Novel nucleophilic reactivity of disulfido ligands coordinated parallel to M-M (M = Rh, Ir) bonds.

Reaction of trans-[(MCp)(2)(mu-CH(2))(2)Cl(2)] (M = Rh, Ir; Cp = eta(5)-C(5)Me(5)) with Li(2)S(2) afforded the disulfido complexes [(MCp)(2)(mu-CH(2))(2)(mu-S(2)-S:S')] which were easily oxidized by O(2) to give the oxygenated complexes [(MCp)(2)(mu-CH(2))(2)(mu-SSO(2)-S:S')]. Although [(RhCp)(2)(mu-CH(2))(2)(mu-S(2)-S:S')] gave a complicated mixture when reacted with CH(2)Cl(2) or CHCl(3), [(IrCp)(2)(mu-CH(2))(2)(mu-S(2)-S:S')] reacted with both CH(2)Cl(2) and CHCl(3) to give the dithioformato complex [(IrCp)(2)(mu-CH(2))(2)(mu-S(2)CH-S:S')]Cl and the cyclotetrasulfido complex [((IrCp)(2)(mu-CH(2))(2))(2)(mu-S(4)-S:S':S":S"')]Cl(2). The oxygenated complexes [(RhCp)(2)(mu-CH(2))(2)(mu-SSO(2)-S:S')] reacted with hydrocarbyl halides to afford bridging hydrocarbyl thiolato complexes accompanied by the generation of SO(2) gas. These complexes have been characterized by NMR spectroscopy, ESI-MS, and X-ray diffraction.

Light-Promoted Addition of Alkenes, Dienes, C60, and Disulfur to the Disulfido Ligand in the Complex CpMoMn(CO)5(μ-S2)

The alkenes, cis-butene, C12H8 (acenaphthylene), and dienes, 1,3-butadiene and cyclopentadiene, were found to add to the mixed-metal disulfido complex CpMoMn(CO)5(μ-S2), 1, in the presence of irradiation by visible light to yield the new compounds CpMoMn(CO)5[μ-S2CH(CH3)CH(CH3)], 2, CpMoMn(CO)5(μ-S2C12H8), 3, CpMoMn(CO)5[μ-S2CH2CH(CHCH2)], 4, and CpMoMn(CO)5(μ-S2C5H6), 5, by 1,2-insertion of a C−C double bond into the S−S bond of 1. The cis-butene was inserted into the S−S bond with retention of stereochemistry. The reaction of 1 with C60 yielded the complex CpMoMn(CO)5(μ-S2C60), 6, in the presence of room light. A crystallographic study of 6 showed that the C60 was inserted into the S−S bond at one of its 6,6 ring junctions. The reaction of 1 with elemental sulfur yielded the tetrasulfido complex CpMoMn(CO)5(μ-S4), 7, by addition of an S2 group to the disulfido ligand. All new complexes were characterized by single-crystal X-ray diffraction analysis.

A new class of (mu-eta2:eta2-disulfido)dicopper complexes: synthesis, characterization, and disulfido exchange.

Rare examples of (mu-eta2:eta2-disulfido)dicopper complexes have been prepared from Cu(I) and Cu(II) complexes of beta-diketiminate and anilido-imine supporting ligands. A novel byproduct derived from sulfur functionalization of the methine position of a beta-diketiminate ligand was identified. DFT calculations on [(LCu)2X2] (L = beta-diketiminate, X = O or S) complexes rationalize the absence of a bis(mu-sulfido)dicopper isomer, [Cu2(mu-S)2](2+), in the synthetic reactions, yet predict that a [Cu2(mu-S)2](0) core is a stable product of 2-electron reduction of the [Cu2(mu-eta2:eta2-S2)](2+) unit. Exchange of the disulfido ligand was discovered upon reaction of a (mu-eta2:eta2-disulfido)dicopper complex with a Cu(I) reagent.

Metal carbonyl derivatives of 1,4-quinone and 1,4-hydroquinone.

CpMoMn(CO)5(mu-S2), 1 reacts with 1,4-benzoquinone to yield CpMoMn(CO)5(mu-S2C6H2O2), 2 containing a 1,4-quinonedithiolato ligand formed by replacing two of the hydrogen atoms on one of the C-C double bonds of 1,4-benzoquinone with sulfur atoms from the disulfido ligand in 1. Compound 2 was reduced with hydrogen to yield CpMoMn(CO)5[mu-S2C6H2(OH)2], 3 which contains a 1,4-hydroquinonedithiolato ligand. Compound 3 was reoxidized to 2 with ferrocenium hexafluorophosphate.

Synthesis and properties of oligomers of iron–manganese carbonyl complexes with bridging disulfido ligands

The reactions of activated CpFeMn(CO) 7 1a and Cp*FeMn(CO) 7 1b, Cp=C 5Me 5 with thiirane yielded the new dimeric mixed metal disulfido complexes: [CpFeMn(CO) 5(μ 3-S 2)] 2 ( 2) and [Cp*FeMn(CO) 5(μ 3-S 2)] 2 ( 3). Compounds 2 and 3 both contain two triply bridging disulfido ligands. When heated at 40 °C, compound 2 was transformed into a trimeric compound Cp 3Fe 3Mn 3(CO) 15(μ 3-S 2)(μ 4-S 2) 2, 4. Compound 4 contains three disulfido ligands, each of which has a different bridging coordination mode in the six atom metal cluster. There are three inequivalent CpFe(CO) 2 groupings linked to a central Mn 3(S 2) 3 core by the disulfido ligands. In solution, compound 4 exhibits a dynamical intramolecular exchange process that interconverts two of the three CpFe(CO) 2 groups on the NMR timescale.

The Addition of Platinum and Palladium Groups to the Disulfido Ligand in Cyclopentadienyl Molybdenum-Manganese Carbonyl Complexes

The reaction of the complexes CpMoMn(CO)5(μ-S2), 2a, Cp=C5H5 and Cp*MoMn(CO)5(μ-S2), 2b, Cp*=C5Me5with (PPh3)2Pt(PhC2Ph) yielded the new bis-sulfido mixed metal complexes CpMoMn(CO)5Pt(PPh3)2(μ 3-S)2, 3a and Cp*MoMn(CO)5Pt(PPh3)2(μ 3-S)2, 3b by insertion of a platinum metal grouping into the S–S bond. A mono-phosphine complex, Cp*MoMn(CO)6Pt(PPh3)(μ 3-S)2, 4b was also isolated from the reaction of 2b with (PPh3)2Pt(PhC2Ph). Compounds 3b and 4b were both characterized crystallographically. Both complexes consist of open MoMnPt clusters with a Mo–Mn single bond, Mo–Mn=2.7570(16) A for 3b and Mo–Mn=2.7837(13) A for 4b, and two triply bridging sulfido ligands. The trimetallic complexes CpMo(O)MnPd(PBu t 3)(CO)5(μ 3-S), 5a and Cp*Mo(O)MnPd(PBu t 3)(CO)5(μ 3-S), 5b containing an oxo ligand bonded to molybdenum were obtained from the reaction of 2a–b with Pd(PBu t 3)2. The molecular structure of the 5a was also established crystallographically.

New disulfido molybdenum-manganese complexes exhibit facile addition of small molecules to the sulfur atoms.

The reaction of Mn(2)(CO)(7)(mu-S2) (1) with [CpMo(CO)(3)](2) (Cp = C(5)H(5)) and [Cp*Mo(CO)(3)](2) (Cp* = C(5)(CH(3))(5)) yielded the new mixed-metal disulfide complexes CpMoMn(CO)(5)(mu-S2) (2) and Cp*MoMn(CO)(5)(mu-S2) (3) by a metal-metal exchange reaction. Compounds 2 and 3 both contain a bridging disulfido ligand lying perpendicular to the Mo-Mn bond. The bond distances are Mo-Mn = 2.8421(10) and 2.8914(5) A and S-S = 2.042(2) and 1.9973(10) A for 2 and 3, respectively. A tetranuclear metal side product CpMoMn(3)(CO)(13)(mu3-S)(mu4-S) (4) was also isolated from the reaction of 1 with [CpMo(CO)(3)](2). Compounds 2 and 3 react with CO to yield the dithiocarbonato complexes CpMoMn(CO)(5)[mu-SC(=O)S] (5) and Cp*MoMn(CO)(5)[mu-SC(=O)S] (6) by insertion of CO into the S-S bond. Similarly, tert-butylisocyanide was inserted into the S-S bond of 2 and 3 to yield the complexes CpMoMn(CO)(5)[mu-S(C=NBu(t))S] (7) and Cp*MoMn(CO)(5)[mu-S(C=NBu(t))S] (8), respectively. Ethylene and dimethylacetylene dicarboxylate also inserted into the S-S bond of 2 and 3 at room temperature to yield the ethanedithiolato ligand bridged complexes CpMoMn(CO)(5)(mu-SCH(2)CH(2)S) (9), Cp*MoMn(CO)(5)(mu-SCH(2)CH(2)S) (10), CpMoMn(CO)(5)[mu-SC(CO(2)Me)=C(CO(2)Me)S] (11), and Cp*MoMn(CO)(5)[mu-SC(CO(2)Me)=C(CO(2)Me)S] (12). Allene was found to insert into the S-S bond of 2 by using one of its two double bonds to yield the complex CpMoMn(CO)(5)[mu-SCH(2)C(=CH(2))S] (13). The molecular structures of the new complexes 2-7 and 9-13 were established by single-crystal X-ray diffraction analyses.

A disulfide-bridged manganese carbonyl anion: synthesis, structure and reactivity of [Mn 3(CO) 10(μ 3-S 2) 2] −

The reduction of Mn 2(CO) 7(μ-S 2), ( 1) with sodium amalgam in THF provided the new monoanion [Mn 3(CO) 10(μ 3-S 2) 2] −, ( 3) isolated in low yield as the [Ph 3PMe] salt. The reaction of Mn 4(CO) 15(μ 3-S 2)(μ 4-S 2), ( 2) with [Ph 3PMe]I provided the same salt [Ph 3PMe] [ 3] in a good yield, 68%. Anion 3 reacts [CpFe(CO) 2(acetone)]BF 4 to yield the neutral mixed metal complex CpFeMn 3(CO) 12(μ 3-S 2)(μ 4-S 2), ( 4). The structures of [Ph 3PMe] [ 3] and 4 were determined by single crystal X-ray diffraction analyses. The core of the structure of 3 consists of two [Mn(CO) 3] groups bridged by two disulfido ligands in a μ 2–η 2 fashion with an additional [Mn(CO) 4] group that bridges the two disulfido ligands. The CpFe(CO) 2 group in 4 is bonded to a sulfur atom of one of the two disulfido ligands of the anionic grouping of 3.

Disulfides of manganese carbonyl. Synthesis of Mn(2)(CO)(7)(mu-S2) and its reactions with tertiary phosphines and arsines.

The reaction of Mn(2)(CO)(9)(NCMe) with thiirane yielded the sulfidomanganese carbonyl compounds Mn(2)(CO)(7)(mu-S(2)), 2, Mn(4)(CO)(15)(mu(3)-S(2))(mu(4)-S(2)), 3, and Mn(4)(CO)(14)(NCMe)(mu(3)-S(2))(mu(4)-S(2)), 4, by transfer of sulfur from the thiirane to the manganese complex. Compound 3 was obtained in better yield from the reaction of 2 with CO, and compound 4 is obtained from the reaction of 2 with NCMe. The reaction of 2 with PMe(2)Ph yielded the tetramanganese disulfide Mn(4)(CO)(15)(PMe(2)Ph)(2)(mu(3)-S)(2), 5, and S=PMe(2)Ph. The reaction of 5 with PMe(2)Ph yielded Mn(4)(CO)(14)(PMe(2)Ph)(3)(mu(3)-S)(2), 6, by ligand substitution. The reaction of 2 with AsMe(2)Ph yielded the new complexes Mn(4)(CO)(14)(AsMe(2)Ph)(2)(mu(3)-S(2))(2), 7, Mn(4)(CO)(14)(AsMe(2)Ph)(mu(3)-S(2))(mu(4)-S(2)), 8, Mn(6)(CO)(20)(AsMe(2)Ph)(2)(mu(4)-S(2))(3), 9, and Mn(2)(CO)(6)(AsMe(2)Ph)(mu-S(2)), 10. Reaction of 2 with AsPh(3) yielded the monosubstitution derivative Mn(2)(CO)(6)(AsPh(3))(mu-S(2)), 11. Reaction of 7 with PMe(2)Ph yielded Mn(4)(CO)(15)(AsMe(2)Ph)(2)(mu(3)-S)(2), 12. The phosphine analogue of 7, Mn(4)(CO)(14)(PMe(2)Ph)(2)(mu(3)-S(2))(2), 13, was prepared from the reaction of Mn(2)(CO)(9)(PMe(2)Ph) with Me(3)NO and thiirane. Compounds 2-9 and 11-13 were characterized by single-crystal X-ray diffraction. Compound 2 contains a disulfido ligand that bridges two Mn(CO)(3) groups that are joined by a Mn-Mn single bond, 2.6745(5) A in length. A carbonyl ligand bridges the Mn-Mn bond. Compounds 3 and 4 contain four manganese atoms with one triply bridging and one quadruply bridging disulfido ligand. Compounds 5 and 6 contain four manganese atoms with two triply bridging sulfido ligands. Compound 9 contains three quadruply bridging disulfido ligands imbedded in a cluster of six manganese atoms.

Reactions of thioethers with Mn(2)(CO)(7)(mu-S(2)) proceed with CO displacement and insertion of the sulfur atom into the Mn-Mn bond.

The reaction of Mn(2)(CO)(7)(mu-S(2)) (2) with SMe(2) yielded the new complexes Mn(2)(CO)(6)(mu-S(2))(mu-SMe(2)) (3) and Mn(4)(CO)(14)(SMe(2))(mu(3)-S(2))(mu(4)-S(2)) (4) in 18 and 41% yields, respectively. The reaction of 2 with the cyclic thioether thietane SCH(2)CH(2)CH(2) yielded the new complexes Mn(2)(CO)(6)(mu-S(2))(mu-SCH(2)CH(2)CH(2)) (5) and Mn(4)(CO)(14)(SCH(2)CH(2)CH(2))(mu(3)-S(2))(mu(4)-S(2)) (6) in 12 and 52% yields, respectively, and the reaction of 2 with 1,4,9-trithiacyclododecane (12S3) yielded Mn(2)(CO)(6)(mu-12S3)(mu-S(2)) (7) and Mn(4)(CO)(14)(12S3)(mu(3)-S(2))(mu(4)-S(2)) (8) in 8 and 24% yields, respectively. Compounds 3 and 5-7 were characterized crystallographically. Compounds 3, 5, and 7 have similar structures in which the thioether ligand has replaced the bridging carbonyl ligand of 2 and its sulfur atom has been inserted into the manganese-manganese bond. The two manganese atoms are not mutually bonded, and two Mn(CO)(3) groups are held together through the bridging disulfido ligand and the bridging sulfur atom of the thioether ligand. Compound 6 contains a Mn(4)(mu(3)-S(2))(mu(4)-S(2)) moiety without metal-metal bonds. On the basis of spectroscopic data, compounds 4 and 8 are believed to have similar structures.

Mn(2)(CO)(6)(mu-CO)(mu-S(2)): the simplest disulfide of manganese carbonyl.

The new disulfide Mn2(CO)6(μ-CO)(μ-S2), 1, has been obtained from the reaction of Mn2(CO)9(NCMe) with thiirane. Compound 1 contains two Mn(CO)3 groups joined by a Mn−Mn bond, a bridging disulfido ligand, and one bridging CO ligand. Compound 1 condenses upon reaction with CO to yield Mn4S4(CO)15, 2, but yields the tetramanganese disulfide Mn4S2(CO)15(PMe2Ph)2, 4, and SPMe2Ph in reaction with PMe2Ph.

Replacement of imido by disulfido at the molybdenum(VI) centre: reactivity of bis(imido) complexes [Mo(η 2-S 2CNEt 2) 2(NR) 2] with hydrogen sulfide and Lawesson's reagent: X-ray crystal structure of [Mo(η 2-S 2CNEt 2) 2(η 2-S 2)( N-2,6-Cl 2C 6H 3)

Reactions of molybdenum(VI) bis(imido) complexes [Mo(η 2-S 2CNEt 2) 2(NR) 2] with hydrogen sulfide and Lawesson's reagent, [PS(4-MeOC 6H 4)(μ-S)] 2, have been carried out in an attempt to generate imido–sulfido complexes [Mo(η 2-S 2CNEt 2) 2(NR)(S)], however, while in all cases one imido ligand is lost, imido–disulfido complexes [Mo(η 2-S 2CNEt 2) 2(η 2-S 2)(NR)] are the major products and [Mo(η 2-S 2CNEt 2) 2(η 2-S 2)( N-2,6-Cl 2C 6H 3)] has been characterised crystallographically. The ligands are arranged in a distorted pentagonal bipyramidal configuration with the imido ligand occupying an axial site being characterised by a short MoN bond of 1.747(8) Å and a MoNC( ipso) angle of 164.9(8)°. The disulfido ligand occupies two equatorial sites with a SS bond length of 2.034(5) Å.

Cluster synthesis by the reactions of [Cp′ 2Fe 2S 4] with transition-metal complexes (Cp′=C 5Me 5, 1,3-C 5H 3(SiMe 3) 2)

Cluster synthesis was carried out by the reactions of [Cp′ 2Fe 2S 4] (Cp′=C 5Me 5, 1,3-C 5H 3(SiMe 3) 2) with some transition-metal complexes. The reaction of [Cp* 2Fe 2S 4] (Cp*=C 5Me 5) with [M(CO) 3(MeCN) 3] or [M(CO) 6] (M=Mo, W) resulted in the formation of tetranuclear tetrathiometalate clusters [{Cp*Fe(CO)} 2{M(μ 3-S) 2(μ-S) 2} {M(CO) 4}]. In the reaction, redistribution of S and CO ligands took place between iron and tungsten atoms without losing them. The reaction of [Cp* 2Fe 2S 4] with [Cp*Ru(MeCN) 3](PF 6) gave a tetranuclear cluster [Cp* 4Fe 2Ru 2S 4](PF 6) 2. In contrast, when [Cp S2 2Fe 2S 4] containing a bulky Cp derivative (Cp S2=1,3-C 5H 3(SiMe 3) 2) was used in place of [Cp* 2Fe 2S 4], a trinuclear cluster [(Cp S2Fe) 2(Cp*Ru)S 4](PF 6) was obtained. In the cluster, two disulfido ligands bridged over two iron atoms and one ruthenium atom in μ 3–η 1:η 2:η 2 and μ 3–η 1:η 1:η 2 fashion.

Synthesis and structures of heterometallic trinuclear clusters [CpFe(CO)2]2(μ3-S2)W(CO)5 and Cp2Fe2(CO)3(μ-CO)(μ3-S)W(CO)5 and kinetic study of migration of the W(CO)5 moiety in the disulfido complex

The reaction of CpFe(CO)2Br, NaSH and W(CO)5(THF) gave two Fe2W clusters, one with a µ3-S2 and the other with a µ3-S; in the former cluster W(CO)5 moiety migration on the disulfido ligand was observed by variable-temperature 1H NMR spectroscopy.