Substituted metal carbonyls. Part 25: Unidentate,intramolecular, and intermolecular bridging modes of 1,1′-bis(diphenylphosphino)ferrocene inM 3S2(CO)9 (M = Fe,Ru) cluster derivatives

Carbonyl exchange of Fe₃(₃-S)₂(CO)₉ wioth1,1-bis(diphenylphosphino)ferrocene (dppf) in refluxing THF gives a cluster ligand with a pendant phosphine moiety, Fe₃(₃-S)₂(CO)₈ (gn¹-Ph₂PlC₅H₄)Fe(C₅H₄)P⁴ MePh₂)]1 ^–,4. Addition of 1 to AuCl(SMe₂) gives ClAu(-dppf) Fe₄(₃-S)₂(CO)₈,8 (45%). Spectroscopic evidence is also obtained for (OC)₈ (₃-S)₂Fe₃(-dppf) Os₃(CO)₁₁,7 and PdCl₂[(-dppf)Fe₃(₃-D)₂(CO)₈]₂,9, from1 and Os₃(CO)₁₁(CH₃CN) and PdCl₂CN)₂, respectively. Crystal data dor3: space group P2₁/n,a = 10.891(3) Å,b = 19.939(3) Å,c = 20.443(2) Å, 100.17(2)°.Z = 4, 3917 reflections,R = 0.049.     

Remetalation processes upon the formation of magnetically active heterometallic sulfide-bridged clusters

The processes of formation of antiferromagnetic heterometallic trinuclear clusters Cp₂Cr₂(-SCMe₃)₂(₃-S)₂ML _n (ML _n = Re(CO)(NO), W(NO)₂, W(NO)Cl, and W(NO)(SCMe₃)) from the antiferromagnetic binuclear chromium(iii) complex Cp₂Cr₂(-SCMe₃)₂(-S) (1) and nitrosyl-containing halide derivatives of Re^I and W⁰ were considered. It is shown that adducts of1 with ML _m (ML _m = Re(NO)(CO)₂Cl₂, W(NO)₂C1₂·1, and W₂(NO)₂(CO)₄I₂) are formed at the first stage. Then they loose the CpCrHal₂ moiety and transform into the reactive remetalation products, CpCr((-SCMe₃)₂(-S)ML _x (M = Re and W). The latter complexes join the electron-deficient CpCrS moiety to generate triangular clusters. The magnetic behavior of antiferromagnetic adducts and triangular clusters is discussed, and the existence of correlations between the energy of spin-spin exchange (–2J(Cr-Cr)) and Cr-Cr and Cr-S(sulfide) bond lengths is mentioned.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2337–2348, December, 1995.     

Synthesis,molecular structures,and thermal decomposition of heterometallic (π-cyclooctadiene)platinum-bis(tricarbonyliron-μ3-chalcogenides)[Fe—Fe], (π-C8H12)Pt(μ3-X)2Fe2(CO)6, where X = S,Se, or Te

Transmetallation of the Fe₃(₃-X)₂(CO)₉ clusters (X = S, Se, or Te) under the action of (-C₈H₁₂)PtCl₂ afforded new heterometallic clusters (-C₈H₁₂)Pt(₃-X)₂Fe₂(CO)₆ (2—4, respectively), which were characterized by X-ray diffraction analysis. The (-C₈H₁₂)Pt fragment in these clusters is bound to two ₃-bridging chalcogen atoms X. The iron atoms are linked to each other. The coordination environment about the Pt atom is planar-square; the Pt...Fe distance is larger than 3.2 . In the synthesis of cluster 4, a new Pt complex was also obtained for which the structure (CO)₂Pt(-Te)₂Pt(CO)₂ (5) was proposed. According to the results of differential scanning calorimetry, thermal decomposition of complex 5 gave rise only to PtTe, whereas complexes 1—4 gave products with the empirical formula Fe₂PtX₂C₂O₂. The influence of the steric effects on the geometry of the clusters is discussed.     

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(-S₂), 2a, Cp=C₅H₅ and Cp*MoMn(CO)₅(-S₂), 2b, Cp*=C₅Me₅with (PPh₃)₂Pt(PhC₂Ph) yielded the new bis-sulfido mixed metal complexes CpMoMn(CO)₅Pt(PPh₃)₂( ₃-S)₂, 3a and Cp*MoMn(CO)₅Pt(PPh₃)₂( 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)( 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) Å for 3b and Mo–Mn=2.7837(13) Å for 4b, and two triply bridging sulfido ligands. The trimetallic complexes CpMo(O)MnPd(PBu ^t ₃)(CO)₅( ₃-S), 5a and Cp*Mo(O)MnPd(PBu ^t ₃)(CO)₅( 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.     

Coupling insertion reactions of diphenylbuta-1, 4-diyne into iron-carbene bonds of [Fe2(CO)7{μ-C(Ph)C(NEt2}]. Syntheses and reactivities of the ferracyclopentadiene [Fe2(CO)6{C(Ph)C(NEt2)C(Ph)C(C2Ph)}] with [Fe2(CO)9]

The diiron ynamine complex [Fe₂(CO)₇{-C(Ph)C(NEt₂)}] (1) reacts with the diphenylbuta-1, 4-diyne, PhCC-CCPh, in refluxing hexane to yield three isomer complexes [Fe₂(CO)₆{C(Ph)C(NEt₂)C(Ph)C(C₂Ph}] (2a), [Fe₂(CO)₆{C(Ph)C(NEt₂)C(C₂Ph)C(Ph)}] (2b), and [Fe₂(CO)₆{NEt₂)C(Ph)C(C₂)C(Ph)}] (2c) All three compounds were identified by their¹H NMR spectra. Compounds2a and2c were characterized by single crystal X-ray diffraction analyses. Crystal data: for2a: space group = P2₁/n,a = 17.873(1) Å, = 18.388(6) Å,c = 9.429(3) Å = 91.99(3)°,Z = 4.3751 reflections,R = 0.044; for2c: space group = P2₁/n,a = 40.58(2) å,b = 12.101(9) Å,c = 12.551(5) Å, = 94.29(7)°,Z = 8.4723 reflection,R = 0.076. Complexes2a and2b result from a [2 + 2] cycloaddition between one of the CC triple bonds of the diyne ligand and the FeC carbene bond, whereas2c results from insertion of one of the CC group into the bridging carbene. Addition of [Fe₂(CO)₉] on2a gave two major products, the tripledecker [Fe₃(CO)₈{C(Ph)C(NEt₂)C(C₂Ph)}], (3 and a tetrairon cluster [Fe₄(CO)₁₁{C(Ph)C(NEt₂)C(Ph)C(C₂Ph)}] (4). Both compounds were characterized by single crystal diffraction analyses. Crystal data: for3: space group = P2₁/n,a = 12.039(3) Å,b = 18.046(3) å,c = 15.270(2) Å, = 90.11(2)°,Z = 4, 1430 reflections,R = 0.067; for4 space group = C2/c,a = 18.633(3) Å,b = 21.467(1)_Å,c = 20.742(2) Å, = 115.03(8)°,Z = 8.992 reflections, R = 0.076. Complex4 is based on a spiked triangular cluster with the alkynyl triple bond attached in ₃-parallel mode on the triangular grouping.     

Synthesis,reactivity and x-ray crystal structures of mixed thiazolato- or carboxylato- carbonyl(phosphine) rhenium(I) complexes

Summary The compound [Re(CO)₃(PPh₃)₂Cl] reacts with the lithium salt of thiazole derivatives (L¹H = 2-amino-benzothiazole, L²H = 2–N-methyl-aminothiazole, L³H = 2–N-phenylaminothiazole, L⁴H = 2–N-(4-methoxyphenyl)aminothiazole, L⁵H = 2–N(4-nitrophenyl)aminothiazole) to give [Re(CO)₂-(PPh₃)₂(L)]. The compounds have been characterized by elemental analysis, i.r. and¹H n.m.r. spectra. At room temperature [Re(CO)₂(PPh₃)(L²)] reacts with L⁶H (L⁶H = diphenylacetic acid), to give the carboxylato complex [Re(CO)₂ .The crystal structures of [Re(CO)₂(PPh₃)₂(L²)] (2) and [Re(CO)₂(PPh₃)₂(L⁶)] (6) were determined by x-ray crystallography. [Re(CO)₂(PPh₃)₂(L²)] crystallizes in the monoclinic space group P2₁/m witha = 9.16(1),b= 24.82(2),c =9.12(1) Å, and = 115.81(4)°; D_c = 1.56 g cm^–3for Z = 2.The structure was refined to a final R of 6.4%. The molecules have C_s symmetry. The rhenium atom is six-coordinate with approximately octahedral geometry. The anionic ligand is chelating through the nitrogen atoms and is strictly planar allowing delocalization of the -electron density. [Re(CO)₂(PPh₃)₂(L⁶)] (6) crystallizes in the monoclinic space group P2₁/n witha = 22.203(5),b = 18.651(5),c =10.653(3) Å, = 91.08(3)°, Dc = 1.47 g cm^–3 for Z = 4. The structure was refined to a final R of 4.7%. The complex is monomeric and the rhenium atom is distorted octahedral with two mutuallytrans PPh₃ ligands, twocis CO ligands and one chelating Ph₂CHCO ₂ ^– ion.     

Diacetylenic Derivatives of Fe2(CO)6(μ-EE′): Spectroscopic Investigations of Fe2(CO)6{μ-EC(H) = C(C≡ CMe)E′} (E = E′, E ≠ E′; E, E′ = S, Se, Te)

The diacetylenic adducts, Fe₂(CO)₆{-EC(H) = C(C CMe)E} (E = E, E E; E, E = S, Se, Te) (1–8) have been obtained from the room temperature stirring of Fe₂(CO)₆(-EE) with HC CC CMe in methanol solvent containing sodium acetate. Compounds 1–8 have been characterized by IR and multinuclear NMR (¹H, ¹³C, ⁷⁷Se, and ^l25Te) spectroscopy. Trends in the chemical shifts of ⁷⁷Se and ¹²⁵Te NMR spectra of Fe₂(CO)₆{-EC(H) = C(C CMe)E} with a variation of EE are discussed.     

Diphenyldichalcogenide complexes of iron, chromium and rhenium carbonyls

The substitution of a labile THF ligand in Cr(CO)₅(THF) by the Ph₂Se₂ molecule provided the monomeric complex Cr(CO)₅(Ph₂Se₂) (I). The similar diiodo-tricarbonyl-iron complex (CO)₃FeI₂(Ph₂Se₂) (II) (along with [(CO)₃Fe(??-SePh)₃Fe(CO)₃]⁺(I₅)^? (III) as a by-product) was separated upon the treatment of ??phenylselenyl iodide?? [PhSeI] with iron pentacarbonyl, Fe(CO)₅. Complex II is isostructural with the known tellurium-containing analogue, (CO)₃FeI₂(Te₂Ph₂). The latter have provided the dimeric tellurophenyl bridged iodo-tricarbonyl-iron complex [(CO)₃IFe(??-TePh)]₂ (IV) under action of the excess of Fe(CO)₅. Its bromide analogue [(CO)₃BrFe(??-TePh)]₂ (V) was prepared upon the treatment of PhTeBr with the excess of Fe(CO)₅. The reaction of [PhSeI] with Re(CO)₅Cl afforded only [(CO)₆Re₂(??-I)₂(??-Se₂Ph₂)] (VI) in contrast to the (CO)₃Re(PhTeI)₃(??₃-I) formation in similar known reaction of [PhTeI]. The molecular and crystal structures of I?CVI is discussed.     

Reactions of N-phenyl-o-semiquinonediimine complexes of nickel and platinum with carbonyl-containing low-valence iron and rhenium compounds

The reactions of o-semiquinonediimine complexes M[o-(NH)(NPh)C₆H₄]₂ (M = Ni (1) or Pt (2)) with carbonyl-containing iron and rhenium compounds were studied. The reactions of complexes 1 or 2 with Fe(CO)₅ afforded the Fe₂(CO)₆[-(NH)(NPh)C₆H₄] complex (3) containing the bridging N-phenyl-o-phenylenediamide ligand in high yield. The reaction of the Re(CO)₂(NO)Cl₂(thf) complex with complex 2 gave rise to the unusual mononuclear rhenium(iii) complex, viz., Re(Ph)[-¹-o-(NH)(NHPh)C₆H₄](CO)(NO)Cl₂ (4), no changes in the geometry of N-phenyl-o-phenylenediamine bound to the Re(NO)(CO)₂Cl₂ fragment being observed. The reaction of complex 2 with the Re(CO)₅Cl complex, which has been preliminarily treated with silver triflate, afforded the heterometallic complex (CO)Pt[-N,N-o-(N)(NPh)C₆H₄]₂ReCl[(NH)(NPh)C₆H₄]. The structures of the resulting complexes were established by X-ray diffraction analysis.     

Reactions of ReH3(CO)(PMe2Ph)3 with Metallic Lewis Acids. Synthesis and Structural Characterization of Hydrido-Bridged Heterometallic Rhenium-Gold, Rhenium-Silver, and Rhenium-Copper Complexes

This contribution presents a study of the reactions of ReH₃(CO)(PMe₂Ph)₃ (1) with a variety of metallic Lewis acids of the coinage metals to form hydrido-bridged heterometallic rhenium-gold, rhenium-silver, and rhenium-copper complexes. The reaction of 1 with AuCl(PPh₃) proceeds with elimination of hydrogen to give the hydrido-bridged heterobinuclear rhenium-gold complex (PMe₂Ph)₃(CO)ClRe(-H)Au(PPh₃) (2). In contrast, the reactions of 1 with AgPF₆, [Cu(CH₃CN)₄]PF₆ or CuCl proceed without elimination of hydrogen to give the hydrido-bridged heterotrinuclear rhenium-silver and rhenium-copper complexes [(PMe₂Ph)₃(CO)HRe(-H)₂M(-H)₂ReH(CO)(PMe₂Ph)₃]PF₆ (M=Ag (3), Cu (4)) and the hydrido-bridged heterotetranuclear rhenium-copper complex (PMe₂Ph)₃(CO)HRe(-H)₂Cu(-Cl)₂Cu(-H)₂ReH(CO)(PMe₂Ph)₃ (5), respectively. The molecular structures of compounds 2 and 3 have been determined by single-crystal X-ray diffraction studies. Crystallographic data for 2: monoclinic, space group P2₁2₁2₁, a=12.804(2) Å, b=13.512(2) Å, c=24.312(3) Å, V=4206(1) ų, Z=4, and R=0.042. Crystallographic data for 3: monoclinic, space group C2/c, a=24.212(6) Å, b=13.098(3) Å, c=20.177(5) Å, b=116.40(2)°, V=5732(2) ų, Z=4, and R=0.044. The X-ray crystal structure of 2 exhibits a short contact (2.798(12) Å) between the gold atom and the CO ligand that is primarily bound to the adjacent rhenium atom, suggesting an incipient semibridging relationship.     

Octanuclear Rare-Earth Clusters

The polyoxo rare-earth core (Ln = Y, Gd, and Yb) has been synthesized from the appropriate rare-earth chloride hydrate and K₂Se and Se in dmf (dimethylformamide). The cluster core is ligated with a variety of polyselenido chains in addition to a number of dmf molecules. The structure of the Gd₈(dmf)₁₃(₄-O)(₃-OH)₁₂(Se₃)(Se₄)₂(Se₅)₂ cluster, 1, was determined by X-ray diffraction methods. It is similar to an Eu cluster previously characterized. Two new clusters, Yb₈(dmf)₁₁(₄-O)(₃-OH)₁₂(Se₄)₂(Se₅)₂Cl₂·dmf, 2, and Y₈(dmf)₁₂(₄-O)(₃-OH)₁₂(Se₄)₄Cl₂·6 dmf, 3, have also been synthesized and characterized. Clusters 2 and 3 have the same octanuclear core of rare-earth atoms as the Gd cluster but contain two chloro ligands in two isomeric conformations in place of the Se ₃ ^2- ring in the Gd cluster. The geometry of the Ln ₈ core is described as a triangulated dodecahedron with ₃-OH groups capping the 12 faces. A ₄-O atom centers the cluster with close contacts to four Ln atoms in an approximate tetrahedral arrangement. Pertinent crystallographic data are: Compound 1, monoclinic, , a= 14.410(3) Å, b = 24.439(5) Å, c = 28.927(6) Å, = 101.05(3)°, V = 9998(3) ų, T = 106(2) K, Z = 4; Compound 2, orthorhombic, , a = 17.049(9) Å, b = 24.68(1) Å, c = 45.03(2)Å, V = 18,945(16) ų, T = 153(2) K, Z = 8; Compound 3, monoclinic, C _2h ⁵ -P2₁/c, a =18.728(l) Å, b = 29.263( 1) Å, c = 20.548(1) Å, = 90.144(1)°, V = 11,261(1) ų, T = 153(2) K, Z = 4.     

Synthesis and characterization of the new mixed-metal,mixed-chalcogen clusters Fe2 M(CO)10(μ3-S)(μ3-Te) (M=W,Mo). crystal structure of Fe2W(CO)10(μ3-S)(μ3-Te)

The new clusters Fe₂ M(CO)₁₀(µ₃-S)(µ₃-Te), I (M=W) and 2 (M=Mo) have been isolated from the room temperature reaction of Fe₂(CO)₆(µ-STe) andM(CO)₅(THF) (M=W, Mo), respectively. Compounds1 and2 have been characterized by IR, 125 Te NMR spectroscopy, and elemental analysis. The structure of compound1 has been established by X-ray crystallography. It belongs to the triclinic space groupP witha=6.844(2) Å,b=9.397(2) Å,c=13.681(10) Å, =81.64(2)°,=81360r,=812(2)°,V=861.2(3) ų,Z=2,D _e =2.835 g cm^–3. Full-matrix least-squares refinement of1 converged to R=0.043, andR _w .=0.115. The structure consists of a Fe₂ WSTe square pyramid and the W atom occupies the apical site of the square pyramid.     

Solution structures and dynamic behaviour of some iron chalcogen derivatives

Summary ¹³C-n.m.r. spectra of (-SR)₂Fe₂(CO)₆, (-SR)₂Fe₂(CO)₅P(n-Bu)₃ and (-X)₂Fe₂(CO)₆ (X=S or Se) show that the solid state structure is maintained in solution. N.m.r. evidence indicates that two isomeric species, not separable by means of the usual physicochemical methods, are present for (-SPh)₂Fe₂(CO)₆ with an overwhelming predominance of theanti form. The phosphine substitutes a COtrans to the iron-iron bond. For any of the iron chalcogen derivatives examined, variable temperature¹³C-n.m.r. spectra show that carbonyl exchange occur in one step. The energy barrier for the exchange of carbon monoxide in the phosphine derivative is lower than that in the unsubstituted complex.     

Photoinduced synthesis of the mixed metal “manganese rhenium cubane” [Mn3Re(CO)12(SC6H5)4]

The photoinduced synthesis and spectroscopic properties of the new mixed metal compound [Mn₃Re(CO)₁₂(SC₆H₅)₄] by UV irradiation of a mixture of Mn₂(CO)₁₀, Re₂(CO)₁₀ with S₂(C₆H₅)₂ is described. No mixed sulphur/selenium compounds [M₄(CO)₁₂S_nSe_4?n(C₆H₅)₄] (M = Mn or Re, n = 1–3) could be obtained by analogous photoreactions.     

Syntheses,molecular structures,and thermal decomposition of cyclopentadienyldicarbonylmanganese chalcogenide derivatives

Transmetallation of the dichalcogenide complexes [CpMn(CO)₂]₂(-X₂) (X = S or Se) with M(CO)₅(thf) (M = Cr or W) afforded new heterometallic complexes CpMn(CO)₂(-Se₂)Cr(CO)₅, CpMn(CO)₂(-Se₂)[Cr(CO)₅]₂, CpMn(CO)₂(-X₂)[W(CO)₅]₂ (X = S or Se), and CpMn(CO)₂(-Se₂)[Cr(CO)₅][W(CO)₅]. According to the X-ray diffraction data, their molecular structures contain the cyclic MnX₂ fragments coordinated by one or two M(CO)₅ groups via the X atoms. Study of thermal decomposition of the manganese complexes with different Mn : M : X ratios (M = Cr, W; X = S, Se, Te) by differential scanning calorimetry (DSC) and thermogravimetry demonstrated that this process took place at rather low temperatures (100—400 °C) and was accompanied by complete elimination of the CO groups followed by elimination of the Cp groups. At any metal to chalcogen ratio, the resulting inorganic chalcogenides contained no impurities of metal oxides and carbides.     

Synthesis and Structure of Two Isomers of Re2Os2(CO)14(CNBu t )4: Clusters with Linear ReOs2Re Chains

The complexes (OC)₄(CNBu ^t )ReOs(CO)₃(CNBu ^t )Os(CO)₃(CNBu ^t )Re(CNBu ^t )(CO)₄ (A) and (OC)₃(CNBu ^t )₂ReOs(CO)₄Os(CO)₃(CNBu ^t )Re(CNBu ^t )(CO)₄ (B) have been isolated in low yield from the reaction of Os(CO)₃(CNBu ^t )₂ with Re₂(-H)(--C₂H₃)(CO)₈ in hexane at room temperature. Both compounds have approximately linear ReOs₂Re chains. The Re–Os lengths are in the range 2.9311(7)–2.952(1) Å the Os–Os lengths are 2.875(1) (A) and 2.8759(7) Å (B).     

Selected properties of bi- and trinuclear complexes prepared by the reactions of Ru3(CO)12 with β-substituted oxadienes

The reactions of Ru₃(CO)₁₂with 4-phenylbut-3-an-2-ine (1a), 3-phenyl-1-p-tolylprop-2-an-1-ine (1b), and 1,3-diferrocenylprop-2-an-1-ine (1c) afforded the Ru₂(CO)₆(-H)(O=C(R¹)C(H)=C(R²)) (2) and Ru₃(CO)₈(O=C(R¹)C(H)=C(R²))₂(3) complexes. Dissolution of these complexes in CHCl₃or CH₂Cl₂gave rise to the Ru₂(CO)₄(-Cl)₂(O=C(R¹)C(H)=C(R²)) complexes (4). The thermal transformations of complexes 2and 3in the presence of an excess of the ligand yielded the Ru₂O₂(CO)₄(³-OC(R¹)C(H)(CH₂R²)C(R²)C(H)C(R¹))₂(5) and Ru(CO)₂(O=C(R¹)C(H)=C(R²))₂(6) complexes. Analogous complexes were obtained upon more prolonged heating of the starting reaction mixtures. The structures of complexes 4a, 5a, and 6cwere established by X-ray diffraction analysis and confirmed by spectroscopic data.     

Carbonyl complexes of manganese, rhenium and molybdenum with ethynyliminopyridine ligands

[MBr(CO)₅] reacts with m-ethynylphenylamine and pyridine-2-carboxaldehyde in refluxing tetrahydrofuran to give, fac-[MBr(CO)₃(py-2-CHN-C₆H₄-m-(CCH))] (M = Mn, 1a; Re, 2a). The same method affords the tetracarbonyl [Mo(CO)₄{py-2-CHN-C₆H₄-m-(CCH)}] (3a) starting from [Mo(CO)₄(piperidine)₂]; and the methallyl complex [MoCl(η³-C₃H₄Me-2)(CO)₂{py-2-CHN-C₆H₄-m-(CCH)}] (4a) from [MoCl(η³-C₃H₄Me-2)(CO)₂(NCMe)₂]. The use of p-ethynylphenylamine gives the corresponding derivatives (1b, 2b, 3b, and 4b) with the ethynyl substituent in the para-position at the phenyl ring of the iminopyridine. All complexes have been isolated as crystalline solids and characterized by analytical and spectroscopic methods. X-ray determinations, carried out on crystals of 1a, 1b, 2a, 2b, 3b, 4a, and 4b, reveals the same structural type for all compounds with small variations due mainly to the different size of the metal atoms. The reaction of complexes 1a or 2a with dicobalt octacarbonyl affords the tetrahedrane complexes [MBr(CO)₃{py-2-CHN-C₆H₄-m-{(μ-CCH)Co₂(CO)₆}}] (M = Mn, 5; Re, 6), the structures of which have been confirmed by an X-ray determination on a crystal of compound 5.     

Cluster synthesis. 42. The synthesis and crystal and molecular structures of the sulfur-bridged platinum-ruthenium carbonyl cluster compounds PtRu3(CO)9 L(PPh3)(μ3-S)2 (L=CO,PPh3) and PtRu4(CO)12(PPh3)(μ4-S)2

Two new mixed metal cluster complexes PtRu₃(CO)₁₀(PPh₃)(₃-S)₂,3 14% yield and PtRu₃(CO)₉(PPh₃)₂(₃-S)₂,4 23% yield were obtained from the reaction of Ru₃(CO)₉(₃-S)₂,1 with Pt(PPh₃)₂(C₂H₄) at 0°C. The cluster of4 consists of a spiked triangle of four metal atoms with two triply bridging sulfido ligands. The reaction of Ru₄(CO)₁₁(₄-S)₂,2 with Pt(PPh₃)₂(C₂H₄) yielded the expanded mixed-metal cluster complex PtRu₄(CO)₁₂(PPh₃)(₄-S)₂,5 in 12% yield. The structure of the cluster5 can be described as a pentagonal bipyramid of five metal atoms and two sulfido ligands with one metal-metal bond missing. Compounds4 and5 were characterized by a single-crystal X-ray diffraction analyses.