Iridium Insertion to Triosmium Cluster Containing Unsaturated Os–Os Bonds

Treatment of the triosmium hydrido cluster, [Os₃(μ-H)₂(CO)₁₀], with one equivalent of [IrCp*Cl₂]₂ (Cp* = pentamethylcyclopentadiene) in refluxing THF afforded four osmium–iridium clusters, including [Os₃Ir₂(μ-CO)(μ-H)₂(CO)₉(Cp*)₂] (1), [Os₃IrCp*(μ-H)₃(μ-Cl)(CO)₉] (2), [Os₃IrCp*(μ-H)(μ-Cl)(μ-CO)(CO)₉] (3) and [Os₂IrCp*(μ-H)(μ-Cl)(CO)₇] (4), in moderate yields. The reactivity of complex 3 with hydrogen, carbon monoxide, and thallium hexafluorophosphate was studied. Complex 4 was found to react with [Os₃(μ-H)₂(CO)₁₀] to give 2 and 3. All of the new compounds were characterized by conventional spectroscopic methods and single-crystal X-ray analysis. This work is dedicated to Professor Frank Albert Cotton for his pioneering contributions to the chemistry of metal clusters     

Study of allylic rearrangement in (μ-H)Os3(μ-O=CNRCH2CH=CH2)(CO)10 (R=H or CH3) clusters

The migration of the double bond in the allylcarboxamide ligands of (μ-H)Os₃(μ-O=CN RCH₂CH=CH₂) (CO)₁₀ (R=H (1) or CH₃ (2)), (μ-D)Os₃(μ-O=CNDCH₂CH=CH₂) (CO)₁₀, and (μ-H)Os₃(μ-O=CNHCD₂CH=CH₂)(CO)₁₀ clusters was studied by¹H,²H, and¹³C NMR spectroscopy. Neither μ-D nor ND groups in the deuterated complexes are directly involved in prototropic processes of allylic rearrangement. Initially, the deuterium atom of the CD₂ group migrates to the ψ-carbon atom of the allyl fragment to form the −CD=CH-CH₂D propenyl moiety, in which the deuterium and hydrogen atoms are gradually redistributed between the ψ-and β-carbon atoms. The triosmium cluster complexes containing the bridging carboxamide ligands O=CNRR' catalyze the allylic rearrangement ofN-allylacetamide. Based on the data obtained, the probable scheme of the allylic rearrangements in clusters1 and2 was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2182–2186, November, 1999.     

An Electron-Deficient Triosmium Cluster Containing the Thianthrene Ligand: Synthesis, Structure and Reactivity of [Os3(CO)9(μ3-η2-C12H7S2)(μ-H)]

Reaction of [Os₃(CO)₁₀(CH₃CN)₂] with thianthrene at 80 °C leads to the nonacarbonyl dihydride compound [Os₃(CO)₉(μ-3,4-η²-C₁₂H₆S₂)(μ-H)₂] (1) and the 46-electron monohydride compound [Os₃(CO)₉(μ₃-η²-C₁₂H₇S₂)(μ-H)] (2). Compound 2 reacts reversibly with CO to give the CO adduct [Os₃(CO)₁₀(μ-η²-C₁₂H₇S₂)(μ-H)] (3) whereas with PPh₃ it gives the addition product [Os₃(CO)₉)(PPh₃)(μ-η²-C₁₂H₇S₂)(μ-H)] (4) as well as the substitution product 1,2-[Os₃(CO)₁₀((PPh₃)₂] (5) Compound 2 represents a unique example of an electron-deficient triosmium cluster in which the thianthrene ring is bound to cluster by coordination of the sulfur lone pair and a three-center-two-electron bond with the C(2) carbon which bridges the same edge of the triangle as the hydride. Electrochemical and DFT studies which elucidate the electronic properties of 2 are reported. Dedicated to the memory of a great scientist, F. Albert Cotton.     

Photochemical reaction of the heterometallic complex (μ-H)Os3{μ-O2CC5H4Mn(CO)3}(CO)10 with triphenylphosphine

Photolysis of the heterometallic complex (μ-H)Os₃{μ-O₂CC₅H₄Mn(CO)₃}(CO)₁₀ together with PPh₃ results in replacement of the CO groups by PPh₃ both at the Mn atom and in the Os₃ metallocycle to afford the complexes (μ-H)Os₃{μ-O₂CC₅H₄Mn(CO)₂PPh₃}(CO)₁₀, (μ-H)Os₃{μ-O₂CC₅H₄Mn(CO)₃}(CO)₉}(CO)₉PPh₃, and (μ-H)Os₃{μ-O₂CC₅H₄Mn(CO)₂PPh₃}(CO)₉PPh₃ (two isomers). The reaction is also accompanied by the partial removal of the Mn(CO)₃ group followed by the protonation of the cyclopentadienyl group and formation of triosmium clusters (μ-H)Os₃(μ-O₂CC₅H₄R}(CO)₁₀ (R=H, Et). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 746–751, April, 2000.     

Preparation and reactivity of metal-containing monomers 53. Synthesis and stability of a cluster monomer (μ-H)Os3(μ-OCNMe2)(CO)9PPh2CH2CH=CH2 in solution

The stability of the complex (μ-H)Os₃(μ-OCNMe₂)(CO)₉PPh₂CH₂CH=CH₂ (1), which contains a free unsaturated functional group in the terminal ligand PPh₂CH₂CH=CH₂, with respect to isomerization, chelation of the ligand, and other transformations in solutions was examined. No transformations of complex1 were observed in the course of synthesis from (μ-H)Os₃(μ-OCNMe₂)(CO)₉NMe₃ or upon heating in solution. Complex1 as well as complexes (μ-H)Os₃(μ-OCNMe₂)(CO)₉PHPh₂ and (μ-H)Os₃(μ-OCNMe₂)(CO)₉PPh₃, which were formed as admixtures, were isolated in the solid state and identified by¹H,¹H-{³¹P}, and¹H-{¹H} NMR, IR, and Raman spectroscopy and mass spectrometry. For Part 52, see Ref. 1. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1455–1460, August, 2000.     

Reaction of Os3(μ-Cl)2(CO)10 with Ph2PCH2PPh2. The formation of a novel 12-membered macrocycle containing C, P, Cl, and Os atoms in the ring

The reaction of Os₃(μ-Cl)₂(CO)₁₀ (1) with Ph₂PCH₂PPh₂ (dppm) in a toluene solution at 65°C results in novel osmium complexes [Os₃(μ-Cl)₂(CO)₉]₂(dppm) (2) and [Os₃(μ-Cl)₂(CO)₈]₂(dppm)₂ (3). Compounds 2 and 3 were characterized by¹H and³¹P NMR, and IR spectroscopy and their structures were established by X-ray analysis. In both compounds, dppm is a bridging ligand between the two cluster units. Molecule3 can be considered as an unusual 12-membered macrocycle containing C, P, Cl, and Os atoms in the ring. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1844–1851, September, 1998.     

Carbonylate anion [(μ-H)Os<Subscript>3</Subscript>(CO)<Subscript>10</Subscript>L]<Superscript>−</Superscript> as a precursor in the synthesis of heterometallic Os<Subscript>3</Subscript>M clusters

A new method for the synthesis of heterometallic clusters Os₃M is developed. The reactions of hydridocarbonyl cluster (μ-H)₂Os₃(CO)₁₀ (I) with binuclear carbonyls Co₂(CO)₈ and Fe₂(CO)₉ in the presence of 1,4-diazabicyclo[2.2.2]octane (Dabco) afford anionic complexes [Os₃Co(CO)₁₃]⁻ (II) and [HOs₃Fe(CO)₁₃] (III) with the counterion N₂C₆H₁₃⁺. Similar reactions with halide complexes [MCp*Cl₂]₂ (M = Rh and Ir) yield neutral complexes [Os₃M(CO)₁₀(μ-H)(μ-Cl)] (M = Rh(IV) and Ir(V)). The reactions occur rapidly at room temperature with high yields. The newly obtained clusters are characterized by the data of IR and ¹H NMR spectroscopy, elemental analysis, and X-ray diffraction analysis.     

Trinuclear Metal Cluster Complexes Containing Fischer-Type Carbene Group from Oxidative Addition Reactions of Tris( N , N -diethyldithiocarbamato)cobalt with Co2(CO)8 and Ru3(CO)12

Two new Fischer-type carbene-containing trinuclear transition-metal clusters: (μ ₃-S)Co₃(CO)₇[μ, η ²-SCNEt₂] 1 and CoRu₂(CO)₉[μ ₃, η ²-SCNEt₂] 2 were obtained by the reaction of tris(N,N-diethyldithiocarbamato)cobalt with Co₂(CO)₈ and Ru₃(CO)₁₂. These clusters contain thiocarboxamido ligand in different coordination modes. The thiocarboxamido ligand served as monometalated or dimetalated sulfur(diethy1amino) carbene ligand in these clusters. Clusters 1 and 2 were characterized by IR, ¹H NMR, and single-crystal X-ray diffraction.     

Synthesis of optically active hydridocarbonyl triosmium clusters with terpene derivatives as ligands. Molecular structure and absolute configuration of a cluster with a bridging dihydroimidazole ligand

Reactions of the triosmium clusters Os₃(CO)₁₁(NCMe) (1) and Os₃(CO)₁₀(NCMe)₂ (2) with terpene derivatives,viz., (1S,3S,4R,6R)-3-(N,N-dimethylamino)-4-amino-3,7,7-trimethylbicyclo [4.1.0]heptane (3). (3bR,4aR)-(3,4,4-trimethyl-3b,4,4a,5-tetrahydrocyclopropa [3,4]cyclopenta[1,2-c]pyrazol-1-yl)acetic acid (4a), and (3bR,4aR)-3-(3,4,4-trimethyl-3b, 4,4a,5-tetrahydrocyclopropa[3,4]cyclopenta[1,2-c]pyrazol-1-yl)propionic acid (4b), were studied. A complex with the terminally coordinated ligand is formed in the first step of the reaction of diamine3 with cluster1. Heating of the resulting complex is accompanied by activation of one of the methyl groups of the ligand to form diastereomers with the bridging tricyclic dihydroimidazole ligand. One of these diastereomers was studied by X-ray diffraction analysis and its absolute configuration was established. Pyrazolycarboxylic acids react with cluster2 as simple organic acids and are coordinated as a bridge at the Os—Os bond through the carboxyl group. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1447–1454, August, 2000.     

Synthesis and structure of three isomeric cluster complexes (μ-H)Os3μ-O2CC5H4Mn(CO)3(PPh3)2(CO)8

The reaction of (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(CO)₁₀ with PPh₃ in the presence of Me₃NO gave mono- and disubstituted heterometallic complexes (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(PPh₃)(CO)₉ and (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃ (PPh₃)₂(CO)₈. Crystal structure determination was performed for three isomeric cluster complexes (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(PPh₃)₂(CO)₈, which are both geometrical and conformational isomers differing in color. The geometrical isomerism is due to the attachment of the PPh₃ group at different vertices of the Os₃ triangle relative to the O₂CC₅H₄Mn(CO)₃ bridging ligand. The conform ational isomerism implies that the molecules have the same arrangement of ligands and differ only in the values of bond angles between the planar fragments of the clusters.     

Synthesis and Characterization of Tetraosmium Carbonyl Complexes Containing a Bridging CO2 Ligand

Treatment of (thd)H (thd=2,2,6,6-tetramethyl-3,5-heptandionate) with excess Os₃(CO)₁₂ in an autoclave at 180°C gives the formation of a brown metal chain complex [Os₂(CO)₅(thd)₂]₂ (1) and a yellow CO₂ cluster complex [Os₄(-H)(-CO₂)(thd)(CO)₁₃] (2) in low yields. Complex 2 was fully identified by a combination of spectroscopic methods and X-ray diffraction study, showing a unique CO₂ ligand bridging a triosmium metal fragment, Os₃(-H)(CO)₁₀ and a monometallic osmium fragment, Os(CO)₃(thd). Upon treatment of 1 with Me₃NO at an elevated temperature, oxidation of the CO ligand occurred at the position trans to the unique CO₂ ligand on the Os(CO)₃(thd) fragment, giving the formation of a second CO₂ cluster [Os₄(-H)(-CO₂)(thd)(CO)₁₂(NCMe)] (3), which is stabilized by a weakly coordinated acetonitrile molecule.     

Synthesis and Structure of Os5(μ-Cl)2(CO)16(CNBut)2: A Cluster with a “Hook” Arrangement of Metal Atoms

Os₅(-X)₂(CO)₁₆(L)₂ (X=Cl, 1, Br; L=CNBu ^t ) clusters have been prepared by the reaction of Os₃(-X)₂(CO)₁₀ with Os(CO)₄(L) at a 1:2 molar ratio in solution at 60°C. The crystal structure of the chloro compound reveals that the Os₃(-Cl)₂ fragment present in the precursory cluster is maintained in 1 with a coordination site cis to the Cl ligands occupied by the unusual Os(CO)₄Os(CO)₃(L)₂ unit. The resulting hook arrangement of the Os₅ skeleton has not been observed previously. The OsOs lengths are in the range 2.8384(6)–2.8999(6)Å. The OsOs bonds associated with the pendant fragment are both considered dative bonds.     

Preparation and reactivity of metal-containing monomers

Starting with the trinuclear clusters, M₃(CO)₁₂ (where M=Os or Ru), Os₃(CO)₁₁(NCCH₃), Os₃(CO)₁₀(NCCH₃)₂, and (-H)Os₃(-OR)(CO)₁₀ (where R=H or Ph), and polyfunctional organic compounds containing vinyl or allyl groups, a number of cluster monomeric complexes have been synthesized containing ligands with an uncoordinated C=C bond,viz.: (-H)Os₃(-4-Vpy)(CO)₁₀, (-H)Os₃(-O₂CCH=CH₂)(CO)₁₀, (-H)Os₃(-OCNHCH₂CH=CH₂)(CO)₁₀, and (-H)M₃(-SCH₂CH=CH₂)(CO)₁₀. The (-H)Os₃(-4-Vpy)(PPh₃)(CO)₉ complex was investigated by X-ray diffraction analysis.For part 30, seeRuss. Chem. Bull., 1993,42, 1016.Vpy is the vinylpyridine ligand.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1293–1298, July, 1993.     

X-ray and conformation analysis of the new trinuclear cluster of osmium Os3(μ,η2-OCC6H5)(η3-C3H5)(CO)9

The crystal structure of the Os₃(μ,η²-O=CC₆H₅)(η³-C₃H₅)(CO)₉ cluster synthesized by the reaction of the (μ-H)Os₃(μ-O=CC₆H₅)(CO)₁₀ complex with allylamine in chloroform was determined by X-ray analysis. Prolonged storage of the reaction mixture led to N-C bond cleavage in allylamine and η³-addition of the allyl fragment at one of the Os atoms (Os-C 2.246 ?, 2.248 ?, and 2.273 ?). The unit cell parameters of the complex are a = 9.494(1) ?, b = 10.479(1) ?, c = 12.474(2) ?, α = 84.55(1)°, β = 70.08(1)°, γ = 70.72(1)°, V = 1255.8(4), ?³, space group P , Z = 2; C₁₉H₁₀O₁₀Os₃; d _calc = 2.922 g/cm³, 3085 I _hkl > 2σ _I of 3611 collected reflections; R = 0.0252. The structure of Os₃(μ,η²-O=CC₆H₅)(η³-C₃H₅)(CO)₉ is molecular. The plane of the Os₃ triangle and the OsCOOs plane are connected according to the “butterfly” principle with an angle of 103.4° between them. The Os-Os distances in the cluster core vary from 2.836(1) ? to 2.844(1) ?; the Os-C_carb distances are 1.88(1)–1.97(1) ?; the distances to the atoms of the bridging ligands are Os-C 2.11(1) ?, Os-O 2.14(1) ?; the O-C bridging bond is 1.24(1) ?. of the Os₃(μ,η²-O=CC₆H₅)(η³-C₃H₅)(CO)₉ triosmium cluster were studied theoretically. The potential curve of the internal rotation of the allyl ligand relative to the Os(1)-C(9) bond was determined. The rotation barrier of the allyl ligand in crystal relative to the Os(1)-C(9) bond is 8.38 kJ/mol, and the rotation of the ligand is not hindered. The effects of the intra-and intermolecular interactions on the conformation state of the cluster complex are considered. Original Russian Text Copyright ? 2008 by V. A. Maksakov, N. V. Pervukhina, N. V. Podberezskaya, M. Yu. Afonin, V. A. Potemkin, and V. P. Kirin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 5, pp. 926–932, September–October, 2008.     

Bridging allyl ligands upon allene insertion into electron-deficient triosmium-hydride clusters [Os3(CO)9(μ3-NSC7H3R)(μ-H)] (R = H, Me)

Allene reacts with the benzothiazolide clusters [Os₃(CO)₉(μ₃-NSC₇H₃R)(μ-H)] (R = H, Me) to afford the bridging allyl complexes [Os₃(CO)₇(μ-CO)₂(μ-NSC₇H₃R)(μ-η¹:η²:η¹-CH₂CHCH₂)] resulting from insertion of allene into the metal-hydride. Both have been crystallographically characterized and differ with respect to the relative arrangement of allyl and benzothiazolide at the triosmium centre.     

Intramolecular Cyclization of Butadiyne Functionalized Ligands coordinated to Triosmium‐Carbonyl Cluster

Reactions between diynes and [Os₃(CO)₁₁(CH₃CN)] in the presence of water give rise to the formation of intriguing hydride triosmium clusters [Os₃(μ‐H)(CO)₉{μ₃,η¹:η³:η¹‐RC₂COHC≡CR}] ( 1a – 1c ) under mild conditions in high yields. When these allylic alcohol compounds 1a – 1c are dissolved in dry polar and donor solvents, an intramolecular cyclization process takes place to give [Os₃(μ‐H)(CO)₉{μ₃,η¹:η³:η¹‐RC₂CH=COCR}] ( 2a – 2c ) in quantitative yield. The utilization of [Os₃(CO)₁₁(CH₃CN)] as starting material together with the addition of water can replace the inconvenient use of [Os₃(μ‐H)₂(CO)₁₀]. This method of synthesis provides a facile pathway for diyne cyclizations and has a clear advantage over those described to date in the literature. Additionally, the analogous cyclized mixed‐metal complex [Os₃(μ‐H)(CO)₉{μ₃,η¹:η³:η¹‐FcC₂CH=COCFc}] ( 2d ) (Fc = ferrocenyl), was synthesized in order to carry out a comparative electrochemical study with the related compounds [Os₃(CO)₁₁(μ₃‐FcC₄Fc)] ( I ) and [Os₃(CO)₁₀(μ₃‐FcC₄Fc)] ( II ), which were previously reported by R. D. Adams.     

Preparation and Structures of Several Complexes Containing Carbon-Rich Ligands Attached to Polynuclear Metal Carbonyls

Several new gold-containing cluster complexes have been prepared from the reactions of gold alkynyl complexes, L _n M-C _x -Au(PPh₃), (x = 3, 4, 6) with Ru₃(CO)₁₀(NCMe)₂. The bis-cluster complex 1,4-{AuRu₃(CO)₉(PPh₃)(μ₃-C₂)}₂C₆H₄ was obtained from Ru₃(CO)₁₀(NCMe)₂ and 1,4-{(Ph₃P)Au(C≡C)}₂C₆H₄. The complexes Ru₃(μ-H){μ₃-C₂C≡C[Ru(PP)Cp′]}(CO)₉ [PP = (PPh₃)₂, Cp′ = Cp; PP = dppe, Cp′ = Cp*] were also obtained as minor by-products and synthesised independently from Ru(C≡CC≡CH)(PP)Cp′. A reaction between Co₃{μ₃-CC≡CC≡CAu(PPh₃)}(μ-dppm)(CO)₇ and Ru₃(CO)₁₂ afforded {(Ph₃P)(OC)₉AuRu₃}C≡CC≡CC{Co₃(μ-dppm)(CO)₇} 7. Related complexes AuRu₃{μ₃-C₂C≡[M(CO)₂Tp]}(CO)₉(PPh₃) (M = Mo 8, W 9) were obtained from {Tp(OC)₂M}≡CC≡C{Au(PPh₃)}, while the mixed metal cluster complexes MoM₂(C₂Me)(CO)₈Tp (M = Ru 13, Fe 14) were obtained from M(≡CC≡CSiMe₃)(CO)₂Tp (M = Mo, W) with Fe₂(CO)₉ and Ru₃(CO)₁₂, respectively. Reactions of the Mo carbyne complex with Co₂(LL)(CO)₆ [LL = (CO)₂, μ-dppm] or nickelocene afforded complexes 15–17 in which Co₂ and Ni₂ fragments, respectively, had coordinated to the C≡C triple bond. XRD structural determinations of 7, 8, 14, 16 and {Tp(OC)₂W}≡CC≡CC≡{Co₃(μ-dppm)(CO)₇} (18-W) are reported. In memoriam: F. Albert Cotton (1930–2007).     

Triosmium carbonyl clusters of sulfur and oxygen mixed donor ligands

The reaction of the lightly stablized cluster [Os₃(CO)₁₀(NCMe)₂] with thiosalicylic acid affords two products [{Os₃(CO)₁₀(µ-H}]₂SC₆H₄CO₂],1 and [Os₃H(CO)10SC₆,H₄C(O)OOs₃H(CO)₁₁],2. Complex 2 undergoes CO dissociation to give1 or fragmentation to give [Os₃H(CO)10SC₆H₄ COOH], 3 in solution. Reaction of phthalic acid and [ Os₃(CO)₁₀(NCMc)₂] gives two products [{Os₃(CO)₁₀(µ-H)}₂O₂CC₆H₄CO₂], 4 and [Os₃H(CO)₁₀O₂CC₆ H₄C(O)OOs₃H(CO)₁₁], 5. 5 also undergoes CO dissociation to give4, but no such conversion is observed in the preparation of [{Os₃(CO)₁₀(µH)}₂ (SC₆H₄S)],6 from the reaction betweeno-dithiobenzene and [Os₃(CO)₁₀ (NCMe)₂]. Unlike thiosalicylic acid, treatment of [Os₃(CO)₁₀(NCMe)₂] with 1 equivalent 2,2'-dithiosalicylaldehyde in dichloromethane produces the compounds [Os₃(CO)₁₀(SC₆H₄CHO)₂],7 and [Os₃(CO)₁₀µ-H)(SC₆H₄CHO)].8 in moderate yields which are stable in both the solid state and solution. The mechanism for the formation of1-5 is also proposed. All the clusters1-8 have been fully characterized by conventional spectroscopic methods and the structures of1, 3, 4, 7, and8 have been established by X-ray, crystallography.     

Protonation of Os3(μ-H)(CO)9(μ3-σ,η2-C≡C-R) clusters (R=CMe2OH,C(Me)=CH2)

Protonation of triosmium clusters Os₃(-H)(CO)₉(₃-,²-CC-R) (R=CMe₂OH, C(Me)=CH₂) affords a cationic complex containing a six-electron propargyl ligand which has been detected for the first time.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1144–1145, June, 1993.     

Polynuclear nitrosyl carbonyl ReI complexes with thiolate and sulfide bridges

The reaction of the complex Re₂(CO)₄(NO)₂Cl₄ (1) with NaSCMe₃ (2) (in THF or MeCN, 65–80°C, 24 h) was studied at different ratios of the reagents (from 1∶2 to 1∶6). At the reagent ratio of 1∶2, the binuclear complex Re₂(CO)₄(NO)₂Cl₂(μ-SCMe₃)₂ (3) was obtained as a mixture ofsyn andanti isomers (3a and3b, respectively) containing Re₂S₂ fragments with different structures (the butterfly-like structure in3a and the planar fragment in3b). When the initials were taken in ratios from 1∶4 to 1∶6, two compounds were isolated: the binuclear complex Re₂(CO)₄(NO)₂(μ-SCMe₃)₂(μ-S)4 (cocrystallized as a mixture ofsyn andanti isomers,4a and4b, respectively) and the triangular cluster Re₃(CO)₃(NO)₃(μ-SCMe₃((μ₃-S)(μ₃-Cl) (5). Apparently, complex4 is formed in the course of isolation as a result of elimination of SR₂ from the unstable tetrathiolate dimer Re₂(CO)₄(NO)₂(SCMe₃)₂(μ-SCMe₃)₂ (6). Cluster5 is the product of the reaction between compounds3 and4. Products of interaction of compound6 with silica gel upon column chromatography of the reaction mixture were studied. Four complexes containing hydroxy and oxo bridging groups, (CO)₂(NO)Re(μ-SCMe₃)₂(μ-OH)Re(SCMe₃)(CO)(NO) (7), (CO)₃(NO)₃RE₃(μ-SCMe₃)₃(μ₃-SCME₃)(μ₃-O) (8), [(CO)₂(NO)₂Re₂(SCMe₃)₂(μ-SCMe₃)₂(μ-OH)][Na(THF)(Et₂O)] (9), and [(CO)₂(NO)₂Re₂(SCMe₃)₂(μ-SCMe₃)₂(μ-OH)]₂−[Na(H₂O)₆][H₅O₂] (10), were isolated. The structures of complexes3, 4, 5, 7, 8, 9, and10 were established by X-ray diffraction study. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1030–1044, May, 1998.