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.     

Synthesis and Crystal Structure of an Incomplete Cubane-like Heterobimetallic Cluster [(η5-C5Me5)2Mo2(μ3-S)(μ-S)3(CuCl)]

The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)( μ3-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a=15.563(3), b=8.9547(18), c=17.846(4) (A), β=101.29(3)°, V=2438.9(9) (A)3, Z=4, Dc=1.878 g/cm3, T=193(2) K, C20H30ClCuMo2S4, Mr=689.60, F(000)=1376, μ(MoKα)=2.335 mm–1, S=1.050, R=0.0305 and wR=0.0688 for 4033 observed reflections with Ⅰ ＞ 2σ(Ⅰ). In the structure of 2, one [(η5-C5Me5)2Mo2(μ-S)2S2] moiety and one CuCl unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by oneμ3-S atom, twoμ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519(7) and 2.7689(8) (A), respectively.     

Dimeric uranium complexes with bridging phospholyl ligands. Crystal structure of [{U(η5-C4Me4P)(μ-η5-C4Me4P)(BH4)}2]

In the symmetrical crystal structure of [{U(η⁵-C₄Me₄P)(μ-η⁵,η¹-C₄Me₄P)(BH₄)}₂], the U-P bond distances for the terminal and bridging η⁵-phospholyl ligands are 2.945(3) and 2.995(3) Å respectively, and the U-P (η¹-phospholyl) bond length is equal to 2.996(3) Å; the tridentate borohydride ligands are cis to the (UP)₂ ring. The cis and trans isomers of [{U(Cp¹)(μ-η⁵,η¹C₄ Me₄P)(BH₄)}₂] (Cp¹ = η⁵-C₅Me₅) are in equilibrium in toluene.     

Replacement of terminal and bridging oxo groups by phenylimido groups in (η-C5H5)OMo(μ-O)2OMo(η-C5H5) giving (η-C5H5)(NPh)Mo(μ-NPh)2Mo(NPh)(η-C5H5)

The treatment of (η-C₅H₅)OMo(μ-O)₂MoO(η-C₅H₅) with excess phenylisocyanate at reflux in tetrahydrofuran yields the arylimido-substituted complex (η-C₅H₅)(NPh)Mo(η-NPh)₂Mo(NPh)(η-C₅H₅), which has been characterized by elemental analysis, and mass, IR and ¹H NMR spectra.     

Triphospha-Ferrocenes as Ligands. Crystal Structures of [Fe(η5-C5Me5)(η5-C2 TBu2P3)M(CO)5)], (M= Cr,MO, W) and the Novel ruthenium and Nickel Complexes [Fe(η5-C5Me5) (η5-C2 TBu2P3)Ru3(CO)9] and [Fe(η5-C5Me5)(η5-C2 tBu2P3)Ni(Co)2]2

Abstract

Syntheses and structures of penta- and hexaphosphorus analogues of ferrocene have been described recently¹. Unlike their simple ferrocene analogues, these complexes have further ligating potential towards other transition metal centres by virtue of the availability of the ring phosphorus lone-pair electrons that are not involved in the η⁵-coordination. We now describe the first examples of coordination compounds of the triphospha-ferrocene [Fe(η⁵-C₅Me₅) (η⁵-C₂ ^tBu₂P₃]. In the ruthenium complex [Fe(η⁵-C₅Me₅)(η⁵-C₂ ^tBu₂P₃) Ru₃(CO)₉] ² two adjacent phosphorus atoms of the η⁵-C₂ ^tBu₂P₃ ring are interlinked by a ruthenium carbonyl cluster in which all three ruthenium atoms interact with the phosphorus atoms. The tetrametallic nickel complex [Fe(η⁵-C₅Me₅)(η⁵-C₂ ^tBu₂P₃)Ni(CO)₂]₂ ³ represents the first example of intermolecular interlinkage of two phospha-ferrocene systems by two metal centres.     

Synthesis,Characterization and Crystal Structure of〔Co_2Mo_2(μ-_4-C_2HPh)(μ-CO)_4(CO)_4(η~-5C_5H_4C(O)Me)_2〕

１　ＩＮＴＲＯＤＵＣＴＩＯＮＤｉｍｏｌｙｂｄｅｎｕｍａｌｋｙｎｅｃｏｍｐｌｅｘｅｓ〔Ｍｏ２（μＲ１Ｃ≡ＣＲ２）（ＣＯ）４（η５Ｃ５Ｈ５）２〕ｃａｎｒｅａｃｔｗｉｔｈａｖａｒｉｅｔｙｏｆｒｅａｇｅｎｔｓｓｕｃｈａｓｐｈｏｓｐｈｉｎｅｓ,ｔｈｉｏｌｓ,ｅｌｅｍｅｎｔａｌｓｕｌｆｕｒ,Ｒｕ３（ＣＯ）１２ａｎｄＣｏ２（ＣＯ）８〔１－４〕．Ｉｎｔｈｅｐｒｏｄｕｃｔｓｔｈｅａｌｋｙｎｅｌｉｇａｎｄｉｓｕｓｕａｌｌｙｒｅｔａｉｎｅｄ．Ｓｏｍｅｔｉｍｅｓ,ａｌｋｙｎｅｓｃｉｓｓｉｏｎｏｃｃｕｒｓ．Ｂｅｉｎｇ…     

The reductive dimerization of [W(NCMe)(MeC2Me)2(η-C5H5)]+: Synthesis and X-ray structure of the novel bis(metallacyclopentadiene) complex [W2(μ-σ,σ,η2,η2-C4Me4)2(η-C5H5)2]

Treatment of [W(CO)(MeC₂Me)₂(-C₅H₅)][PF₆] with ONMe₃ in acetonitrile yields [W(NCMe)(MeC₂Me)₂(-C₅H₅)][PF₆] which undergoes irreversible reduction at a Pt electrode in THF. Sodium amalgam reduction of [W(NCMe) (MeC₂Me)₂(-C₅H₅)][PF₆] gives orange crystals of [W₂(µ-,, ², ²-C₄Me₄)₂ (-C₅H₅)₂] X-ray studies on which reveal pairwise alkyne coupling and a novel bis(metallacyclopentadiene) structure.Dedicated to Professor L. F. Dahl on the occasion of his 65th birthday.     

The mechanism of fluxionality of (1,2,7-η3-2-Me-benzyl)(η5-C5H5)Mo(CO)2

It is shown that (1,2,7-η³-2-Me-benzyl)(η⁵-C₅H₅)Mo(CO)₂ exits in solution as one isomer which is fluxional, probably via (7-η¹-2-Me-benzyl)((η⁵-C₅H₅)Mo(CO)₂, with ΔG^≠₃₇₀ = 23.6 ± 1.0 kcal mol⁻¹. In contrast, (1,2,7-η³-3-Me-benzyl)(η⁵-C₅H₅)Mo(CO)₂ exits as two isomers at −20°C, which undergo interconversion at room temperature with ΔG^≠ 15.7 kcal mol⁻¹. This dynamic process is an allyl rotation. It is probable that there is also a low energy [1,5]-sigmatropic shift.     

The preparation of a series of ring-linked derivatives of [Fe2(η-C5H5)2(CO)2(μ-CO)2] starting from [Fe2η5,η5-C5H4CH(NMe3)CH(NMe2)C5H4}(CO)2(μ-CO)2]+ salts

The salts [Fe₂η⁵,η⁵-C₅H₄CH{NMe₃)CH(NMe₂)C₅H₄}(CO)₂(μ-CO)₂][X] (X = I or SO₃CF₃) are the synthetic precursors to a wide range of [Fe₂(η-C₅H₅)₂(CO)₂(μ-CO)₂] derivatives in which the two cyclopentadienyl ligands are joined by a two-carbon bridge.     

Reactions of Unsaturated Quinoline Triosmium Clusters [Os3(CO)9(μ3-η2-C9H5(4-R)N)(μ-H)] (R=Me or H) with Tetramethylthiourea: X-ray Structures of [Os3(CO)8(μ-η2-C9H5(4-Me)N)(η2-SC(NMe2NCH2Me)(μ-H)2] and [Os3(CO)9(μ-η2-C9H6N)(η1-SC(NMe2)2)(μ-H)]

Treatment of the electronically unsaturated 4-methylquinoline triosmium cluster $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu_3\hbox{-}\upeta^{2}\hbox{-}\hbox{C}_{9}\hbox{H}_{5} \hbox{(4-Me)N})(\upmu\hbox{-H})]$ (1) with tetramethylthiourea in refluxing cyclohexane at 81°C gave $[\hbox{Os}_{3}\hbox{(CO)}_{8}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5} \hbox{(4-Me)N})(\upeta^2\hbox{-SC}(\hbox{NMe}_2\hbox{NCH}_2\hbox{Me})(\upmu \hbox{-H})_2]$ (2) and $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5}\hbox{(4-Me)N})(\upeta^1\hbox{-SC}(\hbox{NMe}_2)_2)(\upmu\hbox{-H})]$ (3). In contrast, a similar reaction of the corresponding quinoline compound $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu_{3}\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N})(\upmu\hbox{-H})]$ (4) with tetramethylthiourea afforded $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N})(\upeta^{1}\hbox{-SC(NMe}_{2})_{2})(\upmu\hbox{-H)}]$ (5) as the only product. Compound 2 contains a cyclometallated tetramethylthiourea ligand which is chelating at the rear osmium atom and a quinolyl ligand coordinated to the Os₃ triangle via the nitrogen lone pair and the C(8) atom of the carbocyclic ring. In 3 and 5, the tetramethylthiourea ligand is coordinated at an equatorial site of the osmium atom, which is also bound to the carbon atom of the quinolyl ligand. Compounds 3 and 5 react with PPh₃ at room temperature to give the previously reported phosphine substituted products $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu \hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5}\hbox{(4-Me)N)(PPh}_{3})(\upmu\hbox{-H)}]$ (6) and $[\hbox{Os}_{3}\hbox{(CO}_{9}(\upmu \hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N)(PPh}_{3})(\upmu\hbox{-H)}]$ (7) by the displacement of the tetramethylthiourea ligand.     

The insertion of acetylene into the formal ruthenium-phosphorus bonds of closo-[Ru4(μ4-PPh)2(μ2-CO)(CO)10. Crystal structure of [Ru4(μ4-PPh){μ4-η3-P(Ph)CHCH}(μ2-CO)(CO)10]

Treatment of closo-[Ru₄(μ₄-PPh)₂(μ₂-CO)(CO)₁₀] with acetylene under ambient conditions leads to the insertion of the acetylene into the skeletal framework of the cluster and the formation of [Ru₄(μ₄-PPh){μ₄-η³-P(Ph)CHCH}(μ₂-CO)(CO)₁₀], the structure of which has been determined X-ray crystallographically.     

Syntheses and crystal structures of quadruply bridged Mo2Se4 complexes containing functionalized cyclopentadienyl ligands: trans/anti − (η5-CH3O2CC5H4)2Mo2(μ-Se)2(μ-SeCH2Ph)(μ-SePh) and trans/syn-(η5-C2H5O2CC5H4)2Mo2(μ-Se)2(μ-SePh)2

Two quadruply bridged Mo₂Se₄ complexes trans/anti-(η⁵-CH₃O₂CC₅H₄)₂Mo₂(μ-Se)₂(μ-SeCH₂Ph)(μ-SePh) (1) from reaction of (η⁵-CH₃O₂CC₅H₄)₂Mo₂(CO)₄ with dibenzyldiselenide and trans/syn-(η⁵-C₂H₅O₂ CC₅H₄)₂Mo₂(μ-Se)₂(μ-SePh)₂ (2) from reaction of (η⁵-C₂H₅O₂CC₅H₄)₂Mo₂(CO)₂(μ-SePh)₂ with elemental selenium have been synthesized and characterized by elemental analyses, ¹H NMR and IR spectroscopy and their crystal structures have been unequivocally determined by x-ray diffraction analyses.     

An Improved Synthesis for Novel Hexaruthenium Cluster Compound Bearing Two Quadruply-Bridging CO Ligands: Synthesis, Characterization, and X-Ray Structural Analysis of Ru6(CO)12(μ3-H)(μ-CO) (μ4-η2-CO)2[η5-C5H4(SiMe3)]

The hexaruthenium cluster compound Ru₆(₃-H)(CO)₁₅[C₅H₄(SiMe₃)] (2), possessing two ₄-²-CO ligands and with the Ru[C₅H₄(SiMe₃)] fragment located at the apex of the central tetrahedral framework, was prepared in low yield by refluxing a toluene solution of C₅H₅(SiMe₃) with excess Ru₃(CO)₁₂. This unique complex was characterized by spectroscopic methods and by X-ray structural analysis. The possible mechanism leading to its formation is discussed.     

Synthesis and structures of bridged diruthenium complexes (E)[η5-C5H4)Ru(CO)]2(μ-CO)2 (E = Me2Ge,Me2SiOSiMe2, Me2SiOSiMe2OSiMe2)

A series of bridged diruthenium complexes (E)[(⁵-C₅H₄)Ru(CO)]₂(-CO)₂ (E = Me₂Ge (2); Me₂SiOSiMe₂ (3); Me₂SiOSiMe₂OSiMe₂ (4)) has been prepared by reacting Ru₃(CO)₁₂ with Cp₂E in refluxing heptane. The molecular structures of (2) and (4) have been determined by X-ray diffraction.     

Synthesis and Crystal Structure of the Octametallic Ferrocene Containing Molybdenum(V) Cluster Mo4(μ3-O)4(μ2-O2P(CH2)2Fc)4O4 and Crystal Structure of 1,1′-Bis(Chloromethyl)Ferrocene

The reaction of MoO₂(acac)₂ with 1,1??-[phosphinicobis(methylene)]-ferrocene in ethanol at 120?°C and in the presence of triethylamine results in the octametallic cluster Mo₄(??₃-O)₄(??₂-O₂P(CH₂)₂Fc)₄O₄. If the reaction is carried out in the absence of triethylamine a mixture of products are obtained of which the identity of the compound produced was hypothesized but not definitively established. Mo₄(??₃-O)₄(??₂-O₂P(CH₂)₂Fc)₄O₄ is characterized by IR and ³¹P-NMR spectroscopy along with the single crystal X-ray determination of its structure. The crystal structure of 1,1??-bis(chloromethyl)ferrocene is also detailed.     

Crystal structure of twinned (η5-C5(CH3)4CF3) (η5-C5(CH3)5)Ru

The substituted sandwich complex crystallizes in monoclinic space groupP2₁/m withZ=2. Twinning to the (001) direction with the special conditionc ^*/4a ^* = cos ^* causes systematic superposition of the reciprocal lattices of both domains and results in an apparent unit cell with double volume and the reflection condition (2h)kl, l=2n. The structure solution was obtained with the subset of intensity data for the predominant individuum and converged atR = 0.040,R _w =0.046 for 832 independent observations and 122 variables. The molecules show disorder with respect to the crystallographic mirror plane. The structure is closely related to that of decamethylruthenocene.     

Structure and bonding analysis of dimethylgallyl complexes of iron, ruthenium, and osmium [(η5-C5H5)(CO)2M(GaMe2)] and [(η5-C5H5)(Me3P)2M(GaMe2)

Density functional theory calculations have been performed for the dimethylgallyl complexes of iron, ruthenium, and osmium [(η(5)-C(5)H(5))(L)(2)M(GaMe(2)] (M = Fe, Ru, Os; L = CO, PMe(3)) at the DFT/BP86/TZ2P/ZORA level of theory. The calculated geometry of the iron complex [(η(5)-C(5)H(5))(CO)(2)Fe(GaMe(2))] is in excellent agreement with structurally characterized complex [(η(5)-C(5)H(5))(CO)(2)Fe(Ga(t)Bu(2))]. The Pauling bond order of the optimized structures shows that the M-Ga bonds in these complexes are nearly M-Ga single bond. Upon going from M = Fe to M = Os, the calculated M-Ga bond distance increases, while on substitution of the CO ligand by PMe(3), the calculated M-Ga bond distances decrease. The π-bonding component of the total orbital contribution is significantly smaller than that of σ-bonding. Thus, in these complexes the GaX(2) ligand behaves predominantly as a σ-donor. The contributions of the electrostatic interaction terms ΔE(elstat) are significantly smaller in all gallyl complexes than the covalent bonding ΔE(orb) term. The absolute values of the ΔE(Pauli), ΔE(int), and ΔE(elstat) contributions to the M-Ga bonds increases in both sets of complexes via the order Fe < Ru < Os. The Ga-C(CO) and Ga-P bond distances are smaller than the sum of van der Waal radii and, thus, suggest the presence of weak intermolecular Ga-C(CO) and Ga-P interactions.     

Ligand shift in mixed-cluster complexes: synthesis of alkyne-bridged Co2Mo2 clusters with two triply-bridging sulphur atoms: crystal structure of [Co2Mo2(η5-Cp)2(μ3-S)2(μ4-CF3C2Me)(CO)4]

Reaction of the complexes [(CO)₃Co(μ-RC₂R′)Co(CO)₃] (R = R′ = CF₃; R = Ph, CF₃ and R′ = H) with the MoMo dinuclear derivative [Mo₂Cp₂(μ-SMe)₂(CO)₂] leads to cleavage of both CS and CH bonds with the formation of closo-octahedral Mo₂CO₂C₂ clusters stabilised by a μ₄-η²-bound alkyne. An X-ray diffraction study has shown that the two Mo₂Co faces of the octahedron are capped by triply-bridging sulphur atoms.