Synthesis of [TpRu(CO)(PPh3)]2(μ-CHCHCHCHC6H4CHCHCHCH) from Wittig reactions

Treatment of [Ru(CHCHCH₂PPh₃)X(CO)(PPh₃)₂]⁺ (X=Cl, Br) with KTp (Tp=hydridotris(pyrazolyl)borate) and NaBPh₄ produced [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄. Reaction of RuHCl(CO)(PPh₃)₃ with HCCCH(OEt)₂ produced Ru(CHCHCH(OEt)₂)Cl(CO)(PPh₃)₂, which reacted with KTp to give TpRu(CHCHCHO)(CO)(PPh₃). Treatment of [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄ with NaN(SiMe₃)₂ and benzaldehyde produced TpRu(CHCHCHCHPh)(CO)(PPh₃). The later complex was also produced when TpRu(CHCHCHO)(CO)(PPh₃) was treated with PhCH₂PPh₃Cl/NaN(SiMe₃)₂. The bimetallic complex [TpRu(CO)(PPh₃)]₂(μ-CHCHCHCHC₆H₄CHCHCHCH) was obtained from the reaction of [TpRu(CHCHCH₂PPh₃)(CO)(PPh₃)]BPh₄ with NaN(SiMe₃)₂ and terephthaldicarboxaldehyde.     

Synthesis, Characterization and Crystal Structures of Some Linked Metal Carbonyl Clusters Derived from Diethynyl-Substituted Silane and Disilane Ligands

The use of diethynylsilane, diethynyldisilane and diethynyldisiloxane in the synthesis of some linked metal carbonyl clusters is demonstrated. New dimeric η²-diyne complexes of cobalt [{Co₂(CO)₆}₂(η²-diyne)], ruthenium [{(μ-H)Ru₃(CO)₉}₂(μ₃-η²,η²-diyne)] and osmium [{(μ-CO)Os₃(CO)₉}₂(μ₃-η²-diyne)] {diyne=HC≡CSi(CH₃)₂C≡CH, HC≡CSi(CH₃)₂–Si(CH₃)₂C≡CH, HC≡CSi(CH₃)₂–O–Si(CH₃)₂C≡CH or HC≡CSi(Ph)₂C≡CH} have been prepared in good yields from the reaction of [Co₂(CO)₈], [Ru₃(CO)₁₂] and [Os₃(CO)₁₀(NCMe)₂] with half an equivalent of the appropriate diyne ligand, respectively. All the twelve compounds have been characterized by IR and ¹H NMR spectroscopies and mass spectrometry. The molecular structures of eight of them have been determined by X-ray crystallography. Structurally, each of the tetracobalt species displays two Co₂C₂ cores adopting the pseudo-tetrahedral geometry with the alkyne bond lying essentially perpendicular to the Co–Co vector. For the group 8 ruthenium and osmium analogues, the hexanuclear carbonyl clusters consist of two trinuclear metal cores with the μ₃-η²,η² bonding mode for the acetylene groups in the former case and μ₃-(η²-||) bonding mode in the latter one. Density functional theory was employed to study the electronic structures of these molecules in terms of the nature of the silyl or disilyl unit and its substituents.     

Synthesis and characterization of diiron(I) 1,2-dimethylethanedithiolate complexes with bridging or chelating 1,2-bis(diphenylphosphino)ethylene

The reaction of complex [μ-SCH(CH₃)CH(CH₃)S-μ]Fe₂(CO)₆ (1) with trans-1,2-bis(diphenylphosphino)ethylene (trans-dppv) in the presence of Me₃NO?2H₂O in CH₂Cl₂/CH₃CN afforded complex {[μ-SCH(CH₃)CH(CH₃)S-μ]Fe₂(CO)₅}₂(trans-dppv) (2) with a bridging dppv. Complex [μ-SCH(CH₃)CH(CH₃)S-μ]Fe₂(CO)₄(cis-dppv) (3) was prepared by the reaction of 1 with cis-dppv and Me₃NO?2H₂O. The new complexes 2 and 3 were characterized by elemental analysis, spectroscopy, and X-ray diffraction analysis.     

Syntheses and molecular structures of Ru3(μ-H)(μ3-CPh2CCCCPh)(CO)9 and Ru3{μ3-CPhCHCC(CPh2)CHCPh}(μ-CO)(CO)8

The reaction between Ru₃(μ-H){μ₃-C₂CPh₂(OH)}(CO)₉ and HCCPh, carried out in the presence of HBF₄ · Me₂O, afforded the cluster complexes Ru₃(μ-H)(μ₃-CPh₂CCCCPh)(CO)₉ (5) and Ru₃{μ₃-CPhCHCC(CPh₂)CHCPh}(μ-CO)(CO)₈ (6), both of which were characterised by single-crystal X-ray studies.     

PREPARATION AND CHARACTERIZATION OF CLUSTER COMPLEXES CONTAINING ONE OR TWO C2M2 (M = Co,Mo) CORES

Abstract

The reaction of dipropargylether with Mo₂(C₅H₄R)₂(CO)₄ (R = H, COOCH₂CH₃), prepared by refiuxing a toluene solution of Mo₂(C₅H₄R)₂(CO)₆ (R = H, COOCH₂CH₃), gave dinuclear cluster complexes (HC₂CH₂OCH₂C₂H-μ)[Mo₂(C₅H₄R)₂(CO)₄] [(1): R = H, (2): R = COOCH₂-CH₃] and tetranuclear cluster complexes [Mo₂(C₅H₄R)₂(CO)₄](μ-HC₂CH₂OCH₂C₂H-μ) [Mo₂(C₅H₄R)₂(CO)₄] [(3): R = H, (4): R = COOCH₂CH₃], respectively. When (1) or (2) was treated with an equimolar amount of octacarbonyldicobalt, the new novel tetranuclear cluster complexes [Co₂CO)₆](μ-HC₂CH₂OCH₂C₂H-μ)(Mo₂(C₅H₄R)₂(CO)₄] [(5): R = H, (6): R = COOCH₂CH₃] were obtained. These complexes were characterized by elemental analysis, IR and ¹H NMR spectra. The molecular structure of complex (3 1/2CH₂C1₂) was determined by single-crystal X-ray diffraction methods.     

Synthesis, Characterization and Structural Properties of Some Heterobimetallic Carbonyl Clusters Derived from Diethynylsilane and Diethynyldisilane Ligands

We report the synthesis of some heterobimetallic carbonyl clusters of groups 8 and 9 derived from diethynylsilane and diethynyldisilane ligands. The triosmium carbonyl clusters containing a pendant acetylene unit [(μ-CO)Os₃(CO)₉(μ₃-η²-HC≡C-E-C≡CH)] [E = Si(CH₃)₂, Si(CH₃)₂–Si(CH₃)₂ and SiPh₂] were prepared and subsequently used for mixed-metal cluster formation. New diyne complexes of the type [{(μ-CO)Os₃(CO)₉}{Co₂(CO)₆}(μ₃-η²:η²-diyne)] and [{(μ-CO)Os₃(CO)₉}{(μ-H)Ru₃(CO)₉}(μ₃-η²:μ₃-η², η²-diyne)] [diyne = HC≡CSi(CH₃)₂C≡CH, HC≡CSi(CH₃)₂–Si(CH₃)₂C≡CH or HC≡CSi(Ph)₂C≡CH] have been prepared in good yields from the reaction of [(μ-CO)Os₃(CO)₉(μ₃-η²-HC≡C-E-C≡CH)] with a molar equivalent of [Co₂(CO)₈] and [Ru₃(CO)₁₂], respectively. All the new heterobimetallic compounds have been characterized by IR and ¹H NMR spectroscopy and mass spectrometry. The X-ray crystal structures and computational analyses based on density functional theory of these three molecules have been studied. Structurally, the dicobalt species adopts a pseudo-tetrahedral Co₂C₂ core with the alkyne bond which lies essentially perpendicular to the Co–Co vector. For the mixed osmium–ruthenium analogue, the hexanuclear carbonyl cluster consist of two trinuclear metal cores with the μ₃-(η²-||) bonding mode for the acetylene group in the former case and the μ₃-η², η² bonding mode in the latter one.     

Co-ordination of copper and silver by [Co2{μ-C2(CH2SCH2CH2)2S}(CO)6]

The thiamacrocycle [Co₂{μ-C₂(CH₂SCH₂CH₂)₂S}(CO)₆] reacts with Ag[BF₄] and PPh₃ to afford the fluxional compound [Co₂{μ-C₂(CH₂SCH₂)₂S}(CO)₆(AgPPh₃)][BF₄], the structure of which has been established by X-ray crystallography, and with [Cu(CH₃₋CN)₄][PF₆] to afford [Co₂{μ-C₂(CH₂SCH₂CH₂)₂S}(CO)₆(CuCH₃₋CN)][PF₆], which undergoes phosphine sustitution.     

New acrylate systems: derivatives of β-SF5-acrylic acid

Addition of pentafluorothio bromide, SF₅Br, to ethyl propiolate results in an 1:1 adduct, SF₅CHCBrC(O)OC₂H₅, and a small amount of a 1:2 adduct. The former is converted by reduction to the corresponding β-SF₅-acrylic ester, SF₅CHCHC(O)OC₂H₅. Treatment of SF₅CH₂CBr(CH₃)C(O)OCH₃ with base produces methyl-β-SF₅-methacrylate, SF₅CHC(CH₃)C(O)OCH₃. The preparation and characterization of these new compounds are described.     

Heteronuclear Alkoxide Compounds Containing Copper and Alkaline Earth Metals

The tetrameric Cu(β-diketonate) alkoxide complex [Cu(thd)(OCH₂CH₂OCH₃)]₄ (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate; 1a ) reacts with the alkaline earth metal alkoxides [M(OCH₂CH₂OCH₃)₂] (M = Ca, 2a ; M = Sr, 2b ; M = Ba, 2c ) to yield the heteronuclear compounds [Cu₂M(thd)₃(OCH₂CH₂OCH₃)₃] (M = Ca, 6a ; M = Sr, 6b ). These heterometallic complexes were also obtained in the reaction of 1a and the mixed Ca and Sr complexes of β-diketonate-alkoxide [M_x(thd)_y(OCH₂CH₂OCH₃)_2x?y] (M = Ca, x = 7, y = 6, 3 ; M = Sr, x = 5, y = 3, 4 ), respectively. In comparison, 1a reacts with the analogous [Ba(thd)(OCH₂CH₂OCH₃)] ( 5a ) to yield a[Ba₂Cu₂(thd)₄(OCH₃)₄(HOCH₂CH₂OCH₃)₂] species ( 8a .) The in situ prepared mixed-ligand Ba Compounds [Ba(thd)OR)] (R = CH₂CH₂OCH₂CH₂OCH₃, ( 5b ); R = CH₂CH₂CH₂OCH₃ ( 5c ) react with the corresponding Cu complexes [Cu(thd)(OR)]_n (R = CH₂CH₂OCH₂CH₂OCH₃), n = 4 ( 1b ); R = CH₂CH₂OCH₂CH₂OCH₃ ( 8b ); R = CH₂CH₂CH₂OCH₃ ( 8c ). However, [Cu(hfd)(OCH₂CH₂OCH₃)]₄ (hfd = 1,1,1,5,5,5,-hexafluoroacetylacetonate; 1e ) is converted in the presence of 2a–c to the simple metathesis products [M(hfd)₂] (M = Ca, Sr, Ba) and [Cu(OCH₂CH₂OCH₃)₂]. Crystalline [Ba₂Cu₂(hfd)₂(thd)₂(OCH₂CH₂CH₂OCH₃)₄(HOCH₂CH₂CH₂OCH₃)₂] ( 9 ) was isolated from the reaction of 1a with in situ prepared [Ba((hfd)OCH₂CH₂CH₂OCH₃)] ( 5d ) in 2-, methoxyethanol. X-Ray crystallographic structure determinations are reported for 6a , 6b , 8b , and 8c .     

Electrochemical oxidative addition of chloride to Rh2(μ-dppm)2(CO)2Cl2

The electrochemical oxidation of trans-Rh₂(μ-dppm)₂(CO)₂Cl₂ (dppm = bis (diphenylphosphino)methane) in the presence of chloride has afforded the new dirhodium(II) unsymmetrical complex Rh₂(μ-dppm)₂(μ-Cl)(CO)Cl₃ which is readily converted to the complex [Rh₂(μ-dppm)₂(μ-Co)(μ-Cl)Cl₂]PF₆. This species has been shown to undergo addition reactions with chloride to regenerate [Rh₂(μ-dppm)₂(μ-Cl)Cl₃(CO)], and with carbon monoxide and t-butylisocyanide to give the additional new dirhodium(II) complexes [Rh₂(μ-dppm)₂(μ-Cl)Cl₂(CO)₂]PF₆ and [Rh₂(μ-dppm)₂(μ-Cl)(CNC(CH₃)₃)₂Cl₂]PF₆, respectively. During prolonged exposure to carbon monoxide [Rh₂(μ-dppm)₂(μ-Co)(μ-Cl)Cl₂]PF₆ undergoes reduction with the loss of chloride to give [Rh₂(μ-dppm)₂(μ-Cl)(CO)₂]PF₆.     

A Rare Tetranuclear Thorium(IV) μ4‐Oxo Cluster and Dinuclear Thorium(IV) Complex Assembled by Carbon–Oxygen Bond Activation of 1,2‐Dimethoxyethane (DME)

The synthesis and X‐ray crystal structure of two new multinuclear thorium complexes are reported. The tetranuclear μ₄‐oxo cluster complex Th₄(μ₄‐O)(μ‐Cl)₂I₆[κ²(O,O’)‐μ‐O(CH₂)₂OCH₃]₆ and the dinuclear complex Th₂I₅[κ²(O,O’)‐μ‐O(CH₂)₂OCH₃]₃(DME) (DME=dimethoxyethane) are formed by C?O bond activation of 1,2‐dimethoxyethane (DME) mediated by thorium iodide complexes.     

Synthetic and Structural Studies on Some New Butterfly Fe/S Cluster Complexes Containing 2,6-(CH2)2C5H3N or (CH2)2 Groups

Four new butterfly Fe/S cluster complexes bearing 2,6-(CH₂)₂C₅H₃N or (CH₂)₂ groups, as the active site models of [FeFe]-hydrogenase, have been prepared by condensation reaction and structurally characterized. Treatments of the parent complex Fe₂(CO)₆[(μ-SCH₂)₂CHCO₂H] (A) with 2,6-(HOCH₂)₂C₅H₃N or HOCH₂CH₂OH in the presence of 4-dimethylaminopyridine and dicyclohexylcarbodiimide afforded the single-butterfly Fe/S complexes Fe₂(CO)₆[(μ-SCH₂)₂CHC(O)OCH₂(2,6-C₅H₃N)CH₂OH] (1) and Fe₂(CO)₆[(μ-SCH₂)₂CHC(O)OCH₂CH₂OH] (3) and the double-butterfly Fe/S complexes [Fe₂(CO)₆(μ-SCH₂)₂CHC(O)OCH₂]₂(2,6-C₅H₃N) (2) and [Fe₂(CO)₆(μ-SCH₂)₂CHC(O)OCH₂]₂ (4). The new complexes 1–4 were fully characterized by elemental analysis, ESI-MS, IR, and ¹H (¹³C) NMR spectroscopy.     

The Reactions of Two New Alkoxy-silyl Functionalized Alkynes with M<Subscript>3</Subscript>(CO)<Subscript>12</Subscript> {M = Fe,Ru} and Co<Subscript>2</Subscript>(CO)<Subscript>8</Subscript>. Spectroscopic Identification of the Products

The new alkoxysilyl-functionalized alkynes [HC≡CCH₂N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] and [HC≡C(C₆H₄)–N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] have been synthesized using literature methods. These have been reacted with Fe₃(CO)₁₂, Ru₃(CO)₁₂ and Co₂(CO)₈. With the iron carbonyl only decomposition was observed: with Ru₃(CO)₁₂ splitting of the alkynes into their parent components and formation of the complexes (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃], (μ-H)Ru₃(CO)₉[C–C(C₆H₄)NH₂] and (μ-H)₂Ru₃(CO)₉[HC–CCH₃] occurred. Finally, with Co₂(CO)₈ formation of complexes Co₂(CO)₆(HC₂R) R=(C₆H₄)NH₂, CH₂NH(CO)NH(CH₂)₃Si(OEt)₃, (C₆H₄)NH(CO)NH(CH₂)₃Si(OEt)₃ containing the intact alkynes could be obtained.     

Studies of metal exchange reactions: the synthesis and structures of heteronuclear metal clusters containing the indenyl ligand (μ3-CR)Co2M(CO)8(η- Ind)(R=H,CH3,C6H5,COOC2H5; M=Mo,W)

The novel tetrahedral clusters (μ₃-CR)Co₂M(CO)₈(η⁵-Ind) (M=Mo,W; R=H, CH₃, C₆H₅, COOC₂H₅) 5-12 containing the indenyl ligand were isolated from reactions of tricobalt clusters (μ₃-CR)Co₃(CO)₉ (R=H, CH₃, C₆H₅, COOC₂H₅) and K(η⁵-Ind)M(CO)₃ (M=Mo,W) under mild conditions. The cluster complex (μ₃-CC₆H₅)CoMo₂(CO)₇(η⁵-Ind)(η⁵-Cp (Cp*=C₅H₄C(O)CH₃) 16 was obtained via the stepwise metal exchange reaction of complex (μ₃-CC₆H₅)Co₂Mo(CO)₈(η⁵-Ind) 9 with Na(η⁵-CpMo(CO)₃, but the reaction of (μ₃-CC₆H₅)Co₂Mo(CO)₈(η⁵-Cp*) 15 with K(η⁵-Ind)Mo(CO)₃ yielded only 9. The crystal structures of compounds 7, 9 and 13 were established by single crystal X-ray diffraction methods and show structural evidence for “slippage” of the indenyl ring.     

Chemie polyfunktioneller Liganden. 66. Reaktionen des 4-Methyl-1,2,6-triarsa-tricyclo[2.2.1.02.6]-heptan mit VIIIb-Metall-Derivaten

Acyl and Alkylidenephosphines. XlX. Molecular and Crystal Structure of 2,4-Bis (dimethyl-amino) ?1,3-diphenyl-l, 3-diphosphetane 4-Methyl-1,2,6-triarsa-tricyclo[2.2.1.0^2.6]-heptan, CH₃C(CH₂As)₃, ( 1 ) reacts with Ru₃(CO)₁₂ to the presumable polymeric [Ru(CO)₄CH₃C(CH₂As)₃]_n ( 2 ), while no reaction takes place with Os₃(CO)₁₂·Os₃(CO)₁₁CH₃CN forms with 1 at ?20°C Os₆(CO)₂₁CH₂As)₃ ( 3 ). The reaction of 1 and Co₂(CO)₈ yields [Co₂(CO)₆CH₃C(CH₂As)₃]_n ( 4 ). 1 and Ir(CO)₂(p-CH₃C₆H₄NH₂)Cl reacts in THF solution to [{Ir(CO)(THF]Cl}₃{CH₃C(CH₂As)₃}₂] ( 5 ), which contains a μ₃-(η²Cη¹O) carbonmonoxide. Upon treatment of [(μ-Cl)Ir(C₈H₁₂)]₂ with 1 [{Ir(C₈H₁₂)Cl}₉{CH₃C(CH₂As)₃}₇] ( 6 ) is obtained. The reaction of 1 with Ir(CO)(PPh₃)₂Cl yields in THF [Ir(CO)(PPh₃)(Cl)CH₃C(CH₂As)₃]₂ · THF ( 7a ). Heating of 7a in CH₂Cl₂ leads to the formation of [Ir(CO)(PPh₃)(Cl)CH₃C(CH₂As)₃ · CH₂Cl₂]₂ ( 7b ). Pt(PPh₃)₃ reacts with 1 in THF to give [Pt(PPh₃)CH₃C(CH₂As)₃]₂ · THF ( 8 ). The novel compounds are mostly insoluble or slightly soluble. They are characterized by elemental and thermogravimetric analysis, IR and, as far as possible, Raman and NMR Spectra. The results indicate that 1 react with the d⁸, d⁹, and d¹⁰ systems of the VIIIb metals under oxidative additions.     

Synthèse de complexes du tungstène,du chrome et du rhénium contenant un ligand 1,4-bidenté carbéne-alcéne

A general synthesis of alkene-carbene complexes of tungsten, chromium and rhenium, containing a six-membered ring system, is outlined and the crystal structure of two new complexes of this type, (CO)₄WC(OEt)(CH)(η²-CH₂CHCH₂) (CH₂CHCH₂) and (CO)₉Re₂(OCH₂CH₃(CH₂(CH₂(CH₂CHCH₂), is described.     

Alkoxide Clusters of Molybdenum and Tungsten as Templates for Organometallic Chemistry: Comparison with Carbonyl Clusters of the Later Transition Elements

Alkoxide and carbonyl ligands complement each other because they both behave as “π buffers” to transition metals. Alkoxides, which are π donors, stabilize early transition metals in high oxidation states by donating electrons into vacant d_π orbitals, whereas carbonyls, which are π acceptors, stabilize later transition elements in their lower oxidation states by accepting electrons from filled d_π orbitals. Both ligands readily form bridges that span M? M bonds. In solution fluxional processes that involve bridge–terminal ligand exchange are common to both alkoxide and carbonyl ligands. The fragments [W(OR)₃], [CpW(CO)₂], [Co(CO)₃], and CH are related by the isolobal analogy. Thus the compounds [(RO)₃W ? W(OR)₃], [Cp(CO)₂W?W(CO)₂Cp], hypothetical [(CO)₃Co?Co(CO)₃], and HC?CH are isolobal. Alkoxide and carbonyl cluster compounds often exhibit striking similarities with respect to substrate binding—e.g., [W₃(μ₃-CR)(OR′)₉] versus [Co₃(μ₃-CR)(CO)₉] and [W₄(C)(NMe)(OiPr)₁₂] versus [Fe₄(C)(CO)₁₃]—but differ with respect to M? M bonding. The carbonyl clusters use e_g-type orbitals for M? M bonding whereas the alkoxide clusters employ t_2g-type orbitals. Another point of difference involves electronic saturation. In general, each metal atom in a metal carbonyl cluster has an 18-electron count; thus, activation of the cluster often requires thermal or photochemical CO expulsion or M? M bond homolysis. Alkoxide clusters, on the other hand, behave as electronically unsaturated species because the π electrons are ligand-centered and the LUMO metal-centered. Also, access to the metal centers may be sterically controlled in metal alkoxide clusters by choice of alkoxide groups whereas ancillary ligands such as tertiary phosphanes or cyclopentadienes must be introduced if steric factors are to be modified in carbonyl clusters. A comparison of the reactivity of alkynes and ethylene with dinuclear alkoxide and carbonyl compounds is presented. For the carbonyl compounds CO ligand loss is a prerequisite for substrate uptake and subsequent activation. For [M₂(OR)₆] compounds (M = Mo and W) the nature of substrate uptake and activation is dependent upon the choice of M and R, leading to a more diverse chemistry.     

Carbonyl substitution chemistry of some trimetallic transition metal cluster complexes with polyfunctional ligands

The trimetallic clusters [Ru₃(CO)₁₀(dppm)], [Ru₃(CO)₁₂] and [RuCo₂(CO)₁₁] react with a number of multifunctional secondary phosphine and tertiary arsine ligands to give products consequent on carbonyl substitution and, in the case of the secondary phosphines, PH activation. The reaction with the unresolved mixed P/S donor, 1-phenylphosphino-2-thio(ethane), HSCH₂CH₂PHPh ( LH₂), gave two products under various conditions which have been characterised by spectroscopic and crystallographic means. These two complexes [Ru₃(μ-dppm)(H)(CO)₇(LH)] and [Ru₃(μ-dppm)(H)(CO)₈(LH)Ru₃(μ-dppm)(CO)₉], show the versatility of the ligand, with it chelating in the former and bridging two Ru₃ units in the latter. The stereogenic centres in the molecules gave rise to complicated spectroscopic data which are consistent with the presence of diastereoisomers. In the case of [Ru₃(CO)₁₂] the reaction with LH₂ gave a poor yield of a tetranuclear butterfly cluster, [Ru₄(CO)₁₀(L)₂], in which two of the ligands bridge opposite hinge wingtip bonds of the cluster. A related ligand, HSCH₂CH₂AsMe(C₆H₄CH₂OMe), reacted with [RuCo₂(CO)₁₁] to give a low yield of the heterobimetallic Ru-Co adduct, [RuCo(CO)₆(SCH₂CH₂AsMe(C₆H₄CH₂OMe))], which appears to be the only one of its type so far structurally characterised.The secondary phosphine, HPMe(C₆H₄(CH₂OMe)) and its oxide HP(O)Me(C₆H₄(CH₂OMe)) also react with the cluster [Ru₃(CO)₁₀(dppm)] to give carbonyl substitution products, [Ru₃(CO)₅(dppm)(μ₂-PMe(C₆H₄CH₂OMe))₄], and [Ru₃H(CO)₇(dppm)(μ₂,η¹-P(O)Me(C₆H₄CH₂OMe))]. The former consists of an open Ru₃ triangle with four phosphide ligands bridging the metal-metal bonds; the latter has the O atom symmetrically bridging one Ru-Ru bond, the P atom being attached to a non-bridged Ru atom.     

Structural studies of diiron complexes with monophosphine ligands tris(4-chlorophenyl)phosphine or diphenyl-2-pyridylphosphine

Four diiron dithiolate complexes with monophosphine ligands have been prepared and structurally characterized. Reactions of (μ-SCH₂CH₂S-μ)Fe₂(CO)₆ or [μ-SCH(CH₃)CH(CH₃)S-μ]Fe₂(CO)₆ with tris(4-chlorophenyl)phosphine or diphenyl-2-pyridylphosphine in the presence of Me₃NO·2H₂O afforded diiron pentacarbonyl complexes with monophosphine ligands (μ-SCH₂CH₂S-μ)Fe₂(CO)₅[P(4-C₆H₄Cl)₃] (1), (μ-SCH₂CH₂S-μ)Fe₂(CO)₅[Ph₂P(2-C₅H₄N)] (2), [μ-SCH(CH₃)CH(CH₃)S-μ]Fe₂(CO)₅[P(4-C₆H₄Cl)₃] (3), and [μ-SCH(CH₃)CH(CH₃)S-μ]Fe₂(CO)₅[Ph₂P(2-C₅H₄N)] (4) in good yields. Complexes 1–4 were characterized by elemental analysis, ¹H NMR, ³¹P{¹H} NMR and ¹³C{¹H} NMR spectroscopy. Furthermore, the molecular structures of 1–4 were confirmed by X-ray crystallography.     

Binuclear ruthenium complexes of fluorous phosphine ligands: Synthesis, properties, and biphasic catalytic activity. Crystal structure of [Ru(μ-O2CMe)(CO)2P(CH2CH2(CF2)5CF3)3]2

The fluorocarbon soluble, binuclear ruthenium(I) complexes [Ru(μ-O₂CMe)(CO)₂L^F]₂, where L^F is the perfluoroalkyl substituted tertiary phosphine, P(C₆H₄-4-CH₂CH₂(CF₂)₇CF₃)₃, or P(CH₂CH₂(CF₂)₅CF₃)₃, were synthesized and partition coefficients for the complexes in fluorocarbon/hydrocarbon biphases were determined. Catalytic hydrogenation of acetophenone to 1-phenylethanol in benzotrifluoride at 105 °C occured in the presence of either [Ru(μ-O₂CMe)(CO)₂P(C₆H₄-4-CH₂CH₂(CF₂)₇CF₃)₃]₂ (1) or [Ru(μ-O₂CMe)(CO)₂P(CH₂CH₂(CF₂)₅CF₃)₃]₂ (2). The X-ray crystal structure of [Ru(μ-O₂CMe)(CO)₂P(CH₂CH₂(CF₂)₅CF₃)₃]₂ was determined. The compound exhibited discrete regions of fluorous and non-fluorous packing.