Reactions of the Cluster Anion [HRu3(CO)11)]− with Dicyclohexylphosphine: Synthesis and Molecular Structure of H2Ru3(CO)8(PCy2)2 and H2Ru3(CO)6(PCy2)2(HPCy2)2

The cluster anion [HRu₃(CO)₁₁]^- (1) reacts with dicyclohexylphosphine in THF solution to give the anionic derivative [HRu₃(CO)₈(PCy₂)₂]^- (2), protonation of which yields the neutral cluster H₂Ru₃(CO)₈(PCy₂)₂ (3) and, in the presence of excess phosphine, HRu₃(CO)₇(PCy₂)₃ (4). In protic methanol as reaction medium, the reaction of 1 with HPCy₂ gives directly the neutral complex H₂Ru₃(CO)₆(PCy₂)₂(HPCy₂)₂ (5), together with 4. The single-crystal structure X-ray analysis of 3 shows a closed triangular Ru₃ framework. The electron count is in accordance with the EAN rule, but the structure analysis of 5 reveals an open, almost linear Ru₃ skeleton, which is electron-deficient with respect to the EAN rule.     

Studies pertaining to the mechanism of “Pt(PCy3)“ addition. The reaction of MPt(μ-H)(μ-PnPr2)Pt(CO)(PCy3) with Pt(C2H4)2(PCy3)

The reaction of Pt(C₂H₄)₂(PCy₃) with (OC)₄M(μ-H)(μ-PⁿPr₂)Pt(CO)(PCy₃, (1: M  Cr, Mo, W) occurs in a highly specific, kinetically controlled manner to give MPt₂(μ²_MPt-CO)(η²_PtPt-H)(μ²_MPt-PⁿPr₂)(CO)₄ (PCy₃)₂ (5), as the first formed trimer. The trimer 5 (M  Mo, W) isomerizes to give MPt₂(μ²_PtPt-CO) ((μ²_MPtH)(μ²_MPt-PⁿPr₂)(CO)₄)PCy₃)₂ (6) which in turn isomerizes to MPt₂μ²_MPtCO)(μ²_MPt (μ²_PtPt-PⁿPr₂)(CO)₄(PCy₃)₂ (7, as the final isolable product. These results provide a detailed insight into the mechanism of “Pt(PCy₃) addition”, a cluster assembly process.     

Synthesis and ligand substituion chemistry of dinuclear,phosphido-bridged complexes of manganese. X-ray crystal structures of Mn2(μ-H)(μ-Cy2P)(CO)7(PCy2H)(1) and Mn2(μ-H)(μ-Cy2P)(CO)6(PMe32

Reaction of Mn₂ (CO)₁₀ with two equivalents of dicyclohexylphosphine in toluene at 110° produces Mn₂ (μ-H)(μ-Cy₂P)(CO)₇(PCy₂H) (1) in 60% yield. Interaction of 1 with excess trimethylphosphine produces Mn₂(μ-H)(μ-Cy₂P)(CO)₆ (PMe₃)(₂ (2) in 90% yield. The X-ray crystal structures of 1 and 2 have been determined. Both structures contain two Mn atoms bridged by a Cy₂P group and a hydridge. In each case, the metal atoms exhibit distorted octahedral geometry, with the phosphines occupying positions trans to the P atom of the bridging dicyclohexylphosphine. A metal-metal distance of ca. 2.9 Å separates the manganese atoms in both complexes.     

Binary palladium carboxylates with electron-donating and electron-withdrawing substituents in the carboxylate ligand: Synthesis and structural studies. The crystal structures of Pd3(μ-CH2ClCO2)6 · CH2Cl2, Pd3(μ-C6H11CO2)6, and Pd3(μ-CMe3CO2)6

Replacement of the acetate ligands in Pd₃(μ-MeCO₂)₆ in benzene gave complexes of the general formula Pd₃(μ-RCO₂)₆ (R = CF₃, CCl₃, CH₂Cl, Me, cyclo-C₆H₁₁, and CMe₃). The structures of the complexes were determined using IR spectroscopy, ESI mass spectrometry, and X-ray diffraction. It was found that the complexes contain a trinuclear Pd framework and that their spectroscopic and structural parameters depend on the donor-acceptor properties of the substituent in the carboxylate ligand.     

Synthesis of single and double butterfly iron carbonyl complexes by reactions of [(μ-RSe)(μ-CO)Fe2(CO)6]− anions. Crystal structures of (μ-p-MeC6H4Se)[μ-PhCH2N(H)CS]Fe2(CO)6 and [(μ-PhSe)(μ-MeAs)Fe2(CO)6]2

The in situ reactions of the [Et₃NH]⁺ and [MgBr]⁺ salts of [(μ-RSe)(μ-CO)Fe₂(CO)₆]⁻ (1) anions with PhC(Cl)NPh gave single butterfly complexes (μ-RSe)(μ-PhCNPh)Fe₂(CO)₆ (2, R=Ph; 3, R=p-MeC₆H₄; 4, R=Et), whereas those of the [Et₃NH]⁺ salts of 1 with R′NCS afforded single butterfly complexes (μ-RSe)[μ-R′N(H)CS]Fe₂(CO)₆ (5, R=Ph, R′=Ph; 6, R=p-MeC₆H₄ R′=Ph; 7, R=p-MeC₆H₄, R′=PhCO; 8, R=p-MeC₆H₄, R′=PhCH₂). Compound 8 could also be prepared by reaction of the [MgBr]⁺ salt of 1 (R=p-MeC₆H₄) with PhCH₂NCS followed by treatment with CF₃CO₂H. More interestingly, while the [Et₃NH]⁺ salt of 1 (R=Ph) reacted with Et₃OBF₄ to give a carbyne ligand-bridged single butterfly complex (μ-PhSe)(μ-EtOC)Fe₂(CO)₆ (9), reaction of the [Et₃NH]⁺ salt of 1 (R=Ph) with MeAsI₂ produced a MeAsAsMe ligand-bridged double butterfly complex [(μ-PhSe)(μ-MeAs)Fe₂(CO)₆]₂ (10). All the new complexes, 2–10, were characterized by elemental analysis and various spectroscopic methods, for complexes 8 and 10, the structures were also confirmed by X-ray diffraction techniques.     

New electron-deficient alkene and alkyne derivatives of Ru5(μ5-C)(CO)15: The syntheses and crystal structure analyses of Ru5(μ5-C)(CO)13 [C2H2(CO2Me)2] and Ru5(μ5-C)(CO)15 [C2(CO2Me)2]

Treatment of carbido cluster Ru₅(μ ₅-C)(CO)₁₅ with Me₃NO in acetonitrile solution followed by addition of dimethyl maleate or dimethyl acetylene dicarboxylate affords new clusters Ru₅(μ ₅-C)(CO)₁₃[C₂H₂(CO₂Me)₂] (1) and Ru₅(μ ₅-C)(CO)₁₅[C₂(CO₂Me)₂] (2), respectively. Single crystal X-ray structural studies reveal that both complexes contain a wingtip-bridged butterfly pentametallic skeleton. In complex1 the maleate fragment is coordinated to one wingtip Ru atom through its carbon-carbon double bond and to the adjacent Ru atom by the formation of two O → Ru dative bonding interactions, while the acetylene dicarboxylate fragment in2 is best considered as acis-dimetallated alkene, linking one hinge Ru atom and the nearby Ru atom at the bridged position. Crystal data for1: space group P 4₂/n;a=20.199(6),c=13.941(3) Å,Z=8; finalR _F=0.025,R _w=0.026 for 3963 reflections withI>2σ(I). Crystal data for2: space group P2₁/n;a=9.634(3),b=20.062(6),c=17.372(5) Å,β=90.62(2)°,Z=4; finalR _F=0 033,R _w=0.036 for 4683 reflections withI>3σ(I).     

Synthesis and X-ray crystal structure analysis of Fe2(CO)6(μ3-S)2Pd(bipy)

The reaction of Fe₂(CO)₆(μ-S₂),1 withbis(dibenzylideneacetone)-palladium, Pd(dba)₂, in the presence of 2,2′-bipyridine yielded the new compound Fe₂(CO)₆(μ ₃-S)₂Pd(bipy),2 in good yield (66%). Compound2 was characterized by IR,¹H NMR and single-crystal X-ray diffraction analyses. Compound2 contains a Pd(bipy) group that has been inserted into the S-S bond of1. Crystal data for2: space group P2₁/n,a=10.019(2) Å,b=25.414(5) Å,c=7.714(2) Å,β=90.26(2)°,Z=4, 1436 reflections,R=0.023.     

Heterometallic derivatives of [Fe2Cp2(μ-PCy)(μ-CO)(CO)2]: rational synthesis of polynuclear complexes from neutral precursors having pyramidal-phosphinidene bridges

The title complex (Cp = η(5)-C(5)H(5)) reacted with the labile carbonyl complexes [M(CO)(5)(THF)] (M = Cr, Mo, W) and [MnCp'(CO)(2)(THF)] (Cp' = η(5)-C(5)H(4)Me) to give phosphinidene-bridged trimetallic compounds of formula [Fe(2)MCp(2)(μ(3)-PCy)(μ-CO)(CO)(7)] (Cr-P = 2.479(1) ?) and [Fe(2)MnCp(2)Cp'(μ(3)-PCy)(μ-CO)(CO)(4)], respectively, after formation of a new M-P bond in each case, and related heterometallic complexes [Fe(2)MClCp(2)(μ(3)-PCy)(μ-CO)(CO)(2)] (M = Cu, Au; Au-P = 2.262(1) ?) were cleanly formed upon reaction with CuCl or the labile tetrahydrothiophene (THT) complex [AuCl(THT)]. The reaction with [Fe(2)(CO)(9)] proceeded analogously to give the triiron derivative [Fe(3)Cp(2)(μ(3)-PCy)(μ-CO)(CO)(6)] in high yield (new Fe-P bond =2.318(1) ?), along with a small amount of the pentanuclear compound [{Fe(CO)(3)}{(μ(3)-PCy)Fe(2)Cp(2)(μ-CO)(CO)(2)}(2)], the latter displaying a central Fe(CO)(3)P(2) core with a distorted bipyramidal geometry (P-Fe-P = 164.2(1)°). In contrast, the reaction with [Co(2)(CO)(8)] resulted in a full disproportionation process to give the salt [{Co(CO)(3)}{(μ(3)-PCy)Fe(2)Cp(2)(μ-CO)(CO)(2)}(2)][Co(CO)(4)], having a pentanuclear Fe(4)Co cation comparable to the above Fe(5) complex (P-Co-P = 165.3(2)°). The attempted photochemical decarbonylation of the above trinuclear complexes gave results strongly dependent on the added metal fragment. Thus, the irradiation with visible or visible-UV light of the new Fe(3) and Fe(2)Cr species caused no decarbonylation but a tautomerization of the metal framework to give the corresponding isomers [Fe(2)MCp(2)(μ(3)-PCy)(μ-CO)(CO)(n)] now exhibiting a dangling FeCp(CO)(2) moiety (M = Cr, n = 7, Cr-Fe = 2.7370(3) ?; M = Fe, n = 6, new Fe-Fe bond = 2.6092(9) ?) as a result of the cleavage of the Fe-Fe bond in the precursor and subsequent formation of a new M-Fe bond. These processes are reversible, since the new isomers gave back the starting complexes under low (Cr) or moderate (Fe) thermal activation. In contrast, the manganese-diiron complex [Fe(2)MnCp(2)Cp'(μ(3)-PCy)(μ-CO)(CO)(4)] could be decarbonylated stepwise, to give first the tetracarbonyl complex [Fe(2)MnCp(2)Cp'(μ(3)-PCy)(μ-CO)(2)(CO)(2)] and then the tricarbonyl cluster [Fe(2)MnCp(2)Cp'(μ(3)-PCy)(μ-CO)(3)], the latter having a closed triangular metal core (Fe-Fe = 2.568(7) ?; Mn-Fe = 2.684(8) and 2.66(1) ?).     

Reactions of dipropargyl manolate,terephthalate with Co2(CO)8, Mo2Cp2(CO)4 and RuCo2(CO)11 give the di or tetranuclear clusters. The crystal structure of [CH2(CO2CH2C2H-μ)2][Co2(CO)6]2 and [p-(HC2CH2OCO)C6H4(CO2CH2C2H-μ)][Co2(CO)6]

The reactions of dipropargyl manolate and terephthalate, respectively, with Co₂(CO)₈ in THF at room temperature gave four new compounds [R(CO₂CH₂C₂H-μ)₂][Co₂(CO)₆]₂ (R=CH₂, 1a; R=C₆H₄, 1b) and [(HC₂CH₂OCO)R(CO₂CH₂C₂H-μ)][Co₂(CO)₆] (R=CH₂, 2a; R=C₆H₄-1,4-, 2b), and compounds 2a and b reacted with RuCo₂(CO)₁₁ to form two new linked clusters [R(CO₂CH₂C₂H-μ)₂][Co₂(CO)₆][RuCo₂(CO)₉] (R=CH₂, 3a; R=C₆H₄-1,4-, 3b). The treatment of two dipropargyl esters, respectively, with RuCo₂(CO)₁₁ afforded another two new clusters [R(CO₂CH₂C₂H-μ)₂][RuCo₂(CO)₉]₂ (R=CH₂, 4a; R=C₆H₄-1,4-, 4b). The reactions of dipropargyl manolate, terephalate with Mo₂Cp₂(CO)₄ gave rise to the formation of dinuclear complexes [(HC₂CH₂OCO)R(CO₂CH₂C₂H-μ)][Mo₂Cp₂(CO)₄] (R=CH₂, 5a; R=C₆H₄-1,4-, 5b), compound 5a reacted with Co₂(CO)₈ to produce the cluster [CH₂(CO₂CH₂C₂H-μ)₂][Co₂(CO)₆][Mo₂Cp₂(CO)₄] 6a. All the new clusters have been characterized by C/H elemental analysis, IR and ¹H NMR spectroscopies. The structure of [CH₂(CO₂CH₂C₂H-μ)₂][Co₂(CO)₆]₂ 1a and [p-(HC₂CH₂OCO)C₆H₄(CO₂CH₂C₂H-μ)][Co₂(CO)₆] 2b have been determined by single crystal X-ray diffraction methods.     

New triosmium–iridium clusters: Synthesis and molecular structure of [Os3Ir2(Cp1)2(μ-OH)(μ-CO)2(CO)8Cl] (1), [Os3IrCp1(μ-OH)(CO)10Cl] (2), [Os3IrCp1(μ-H)(μ-Cl)(η3,μ3-C5H2N(NH2)Br)(CO)9] (3) and [Os3IrCp1(μ-Cl)2(η2,μ3-C5H3N(NH)Br)(CO)7] (4)

The trinuclear osmium carbonyl cluster, [Os₃(CO)₁₀(MeCN)₂], is allowed to react with 1 equiv. of [IrCp¹Cl₂]₂ (Cp¹ = pentamethylcyclopentadiene) in refluxing dichloromethane to give two new osmium–iridium mixed-metal clusters, [Os₃Ir₂(Cp¹)₂(μ-OH)(μ-CO)₂(CO)₈Cl] (1) and [Os₃IrCp¹(μ-OH)(CO)₁₀Cl] (2), in moderate yields. In the presence of a pyridyl ligand, [C₅H₃N(NH₂)Br], however, the products isolated are different. Two osmium–iridium clusters with different coordination modes of the pyridyl ligand are afforded, [Os₃IrCp¹(μ-H)(μ-Cl)(η³,μ₃-C₅H₂N(NH₂)Br)(CO)₉] (3) and [Os₃IrCp¹(μ-Cl)₂ (η²,μ₃-C₅H₃N(NH)Br)(CO)₇] (4). All of the new compounds are characterized by conventional spectroscopic methods, and their structures are determined by single-crystal X-ray diffraction analysis.     

Hydrothermal synthesis and characterization of LaIII and CuII coordination polymers with 5-nitroisophthalic acid (H2Nip), [La2(μ-Nip)(μ-SO4)2(H2O)5] n and {[Cu3(μ-OH)2(μ-Nip)2(μ-H2O)2] · 2H2O} n

3D La^III and 2D Cu^II coordination polymers with 5-nitroisophthalate anions, [La₂(μ-Nip)(μ-SO₄)₂(H₂O)₅] _n (1) and {[Cu₃(μ-OH)₂(μ-Nip)₂(μ-H₂O)₂] ·?2H₂O} _n (2), have been synthesized, characterized and studied by X-ray crystallography. The La atoms have eight–coordinate geometries in distorted square antiprism environments and the Cu atoms have five- and six–coordinate geometries with distorted square pyramidal and octahedral environments. Self-assembly of these compounds in the solid state occurs through coordination and hydrogen bonding.     

Oxidative addition of OH bond to a metal centre: synthesis and crystal structure of trans-(PhO)(H)Pd(PCy3)2·PhOH

(Cy₃P)₂Pd (Cy = C₆H₁₁) reacts with PhOH in toluene to give the phenoxopalladium(II) hydride derivative trans-(PhO)(H)Pd(PCy₃)₂·PhOH; the crystal structural study has established that the oxygen of the phenoxy group forms a hydrogen bridge with an uncoordinated phenol molecule, and has allowed direct location of the hydride atom (Pd&.sbnd;H, 1.57(2) Å).     

Solid–Gas Hydrogenation of Hex-3-yne and 1,4-Cyclohexadiene in the Presence of Ru3(CO)9(μ-H)(μ-PPh2), Ru3(CO)10(μ-H)(μ-PPh2), Ru3(CO)7(μ-PPh2)2(C6H4), and Ru4(CO)11(μ4-PPh)(C6H4) Deposited on Pyrex Glass, Silica, and Alumina

The title complexes were tested in the hydrogenation of hex-3-yne and of 1,3- and 1,4-cyclohexadiene (CHD) under solid–gas conditions. The clusters were deposited on three “standard” supports, that is, pyrex glass, alumina, and silica. All the clusters, particularly (μ-H)Ru₃(CO)₁₀(PPh₂), show hydrogenation activity. However, they are not particularly selective toward the formation of monoenes; “disproportionation” of 1,3- and 1,4-CHD to hydrogenated products and benzene also occurs. The hydrogenation activity of the clusters is dependent on their nature, the type of substrate, and the characteristics of the supporting material; silica and pyrex glass are usually more active than alumina. Attempts at detecting the formation of organometallic intermediates or by-products (through IR spectroscopy) were made. HRTEM was used to check for eventual decomposition on some supports.     

The preparation and structure of the tetranuclear ruthenium cluster [Ru4(CO)10(μ2-Cl)2(μ3-OEt)2]

The tetranuclear ruthenium cluster [Ru₄(CO)₁₀Cl₂(OEt)₂] has been prepared in low yield by the reaction of [Ru₃(CO)₁₂] with [N(PPh₃)₂]Cl in refluxing EtOH, followed by oxidation with either [NO][BF₄] or Ag[ClO₄]. A single-crystal X-ray analysis of the complex shows that the four metal atoms adopt a planar geometry with one ruthenium bonded by two μ₂-Cl ligands and two μ₃-OEt ligands to a trinuclear fragment. This complex crystallises in the monoclinic space group I2/c, with a 14.458(3), b 22.073(6), c 15.302(4) Å, β 99.54(2)°, Z = 8; 3113 observed data with F > 3σ(F) were refined by blocked full-matrix least squares to R = 0.031, R_w = 0.034.     

C-X bond formation and cleavage in the reactions of the ditungsten hydride complex [W2(η5-C5H5)2(H)(μ-PCy2)(CO)2] with small molecules having multiple C-X bonds (X = C, N, O)

Two molecules of C(2)(CO(2)Me)(2) or isocyanides could be added to the title hydride complex under mild conditions to give dienyl-[W(2)Cp(2){μ-η(1),κ:η(2)-C(CO(2)Me)=C(CO(2)Me)C(CO(2)Me)=CH(CO(2)Me)}(μ-PCy(2))(CO)(2)] (Cp = η(5)-C(5)H(5)), diazadienyl-[W(2)Cp(2){μ-κ,η:κ,η-C{CHN(4-MeO-C(6)H(4))}N(4-MeO-C(6)H(4))}(μ-PCy(2))(CO)(2)] or aminocarbyne-bridged derivatives [W(2)Cp(2){μ-CNH(2,6-Me(2)C(6)H(3))}(μ-PCy(2)){CN(2,6-Me(2)C(6)H(3))}(CO)]. In contrast, its reaction with excess (4-Me-C(6)H(4))C(O)H gave the C-O bond cleavage products [W(2)Cp(2){CH(2)(4-Me-C(6)H(4))}(O)(μ-PCy(2))(CO)(2)] and [W(2)Cp(2){μ-η:η,κ-C(O)CH(2)(4-Me-C(6)H(4))}(O)(μ-PCy(2))(CO)].     

Synthesis and Crystal Structure of Cluster [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6]2

The reaction of dipropargyl phthalate C6H4-1,2-(CO2CH2C2H-μ)2 1 with octacarbonyldicobalt 2 resulted in the formation of red complex [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6]2 3, in which each Co2(CO)6 group coordinates to one of the two C≡C bonds of 1. Molecular structure of complex 3 was determined by single crystal X-ray analyses. The crystal belongs to the monoclinic system, space group P21/a with the following crystallographic parameters: a=8.521(2), b=29.143(6), c=12.918(7)(A), β= 100.12(3)°, V=3158(2)(A)3, Z=4, Mr=814.09, Dc=1.712 g.cm-3, F(000)=1608, μ(Mo-Kα)=21.37 cm-1 and final R=0.044 for 3151 observations.     

Ir(PCy3)2(H)2(H2B-NMe2)]+ as a latent source of aminoborane: probing the role of metal in the dehydrocoupling of H3B⋅NMe2H and retrodimerisation of [H2BNMe2]2

The Ir^III fragment {Ir(PCy₃)₂(H)₂}⁺ has been used to probe the role of the metal centre in the catalytic dehydrocoupling of H₃B?NMe₂H ( A ) to ultimately give dimeric aminoborane [H₂BNMe₂]₂ ( D ). Addition of A to [Ir(PCy₃)₂(H)₂(H₂)₂][BAr^F₄] ( 1 ; Ar^F=(C₆H₃(CF₃)₂), gives the amine‐borane complex [Ir(PCy₃)₂(H)₂(H₃B?NMe₂H)][BAr^F₄] ( 2 a ), which slowly dehydrogenates to afford the aminoborane complex [Ir(PCy₃)₂(H)₂(H₂B? NMe₂)][BAr^F₄] ( 3 ). DFT calculations have been used to probe the mechanism of dehydrogenation and show a pathway featuring sequential BH activation/H₂ loss/NH activation. Addition of D to 1 results in retrodimerisation of D to afford 3 . DFT calculations indicate that this involves metal trapping of the monomer–dimer equilibrium, 2 H₂BNMe₂ ? [H₂BNMe₂]₂. Ruthenium and rhodium analogues also promote this reaction. Addition of MeCN to 3 affords [Ir(PCy₃)₂(H)₂(NCMe)₂][BAr^F₄] ( 6 ) liberating H₂B? NMe₂ ( B ), which then dimerises to give D . This is shown to be a second‐order process. It also allows on‐ and off‐metal coupling processes to be probed. Addition of MeCN to 3 followed by A gives D with no amine‐borane intermediates observed. Addition of A to 3 results in the formation of significant amounts of oligomeric H₃B?NMe₂BH₂?NMe₂H ( C ), which ultimately was converted to D . These results indicate that the metal is involved in both the dehydrogenation of A , to give B , and the oligomerisation reaction to afford C . A mechanism is suggested for this latter process. The reactivity of oligomer C with the Ir complexes is also reported. Addition of excess C to 1 promotes its transformation into D , with 3 observed as the final organometallic product, suggesting a B? N bond cleavage mechanism. Complex 6 does not react with C , but in combination with B oligomer C is consumed to eventually give D , suggesting an additional role for free aminoborane in the formation of D from C .     

Structures, energy bands and conductivities of (Me_3NEt)[Pd(dmit)_2]_2 and (NEt_4)[Pd(dmit)_2]_2

The electrical conductive molecular crystals (Me3NEt)[Pd(dmit)2]2 and (NEt4)[Pd (dmit)2]2 (dmit = 4,5-dimercapto-1,3-dithiole-2-thione) have been prepared, and their crystal structures and conductivity-temperature curves have been determined. The fact that the conductivity at room temperature of (Me3NEt)[Pd(dmit)2]2 (a = 58 Ω· cm-1) is much higher than that of (NEt4)-[Pd(dmit)2]2(cr= 2.2 Q~1 ?cm'1) has been rationally explained by the results of energy band calculations. (MeNEt3)[Pd(dmit)2]2 belongs to monoclinic system, P21/m space group and (NEt4)[Pd (dmit)2]2 belongs to triclinic system, P1 space group. The structural conducting component of the crystals is the planar coordinative anion [Pd(dmit)2]05- which forms the face-to-face dimmer [Pd(dmit)2]2-. These dimers have been further constructed to be a kind of two-dimensional (2-D)conductive molecular sheet by means of S…S intermolecular interactions. The tiny difference of the above 2-D molecular sheets of the two title crystals has resulted in one     

Synthesis and Characterization of Tetrametal Cluster [Co2(CO)6][μ-HC2CH2OCH2C2H-μ][Co2(CO)6]

The treatment of dipropargyl ether HC2CH2OCH2C2H with Co2(CO)8 resulted in the formation of a novel cluster [Co2(CO)6][μ-HC2CH2OCH2C2H-μ][Co2(CO)6]. The cluster was characterized by C/H analyses, IR and 1H NMR spectroscopy and X-ray crystal structure determination. It belongs to monoclinic system, space group P21/c with the following crystallographic parameters: a=18.149(2), b=7.0111(7), c=20.897(2)(A), β=115.318(7)°, V=2403.7(5)(A)3, Z=4, Mr=665.97, Dc=1.840 g·cm-3, F(000)=1304.00, μ(Mo-Kα)=27.76 cm-1 and R=0.030 for 2372 observed reflections.     

Synthesis, Characterization and Crystal Structure of [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2]

The reaction of μ-alkyne-bridged dimolybdenum compound [Mo2(μ-C2HPh)(CO)4(η5-C5H4C(O)Me)2] 1 with Co2(CO)8 in refluxing toluene gave a new butterfly compound [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2] 2 which was fully characterized by elemental analysis, IR, 1H NMR and X-ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C30H20Co2Mo2O10, Mr=850.23, space group P21/a(#14), a=14.165(5), b=12.498(2), c=16.204(2)(A), β = 96.50(2)°, V = 2850(1)(A)3, Z = 4, Dc = 1.981 g cm-3, F(000)=1672, μ(MoKα)=20.41 cm-1, final R=0.030, Rw=0.039 for 4831 observable reflections with I>2σ(I). The structure contains a Co2Mo2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi-bridging carbonyl ligand.