33635-53-9

Upstream product

• 15696-40-9 dodecacarbonyl triosmium 
• 603-35-0 triphenylphosphine 
• 16406-49-8 osmium pentacarbonyl 
• 34766-74-0 Os3(CO)9(μ-C4Ph4) 
• 10170-15-7 trans-{OsCl₂(CO)2(PPh₃)2} 
• 25685-05-6 octacarbonyldihydridodiosmium 
• 85702-39-2 Os₂(CO)8(CH₂CHCO₂CH₃) 
• 34766-74-0 Os3(CO)9(μ-C4Ph4) 
• 12560-48-4 dodecacarbonyldihydridotriosmium 
• 21773-71-7 Br₂Os₃(CO)12 

Downstream Products

• 119850-61-2 {(C₆H₅)3P}(CO)4OsCr(CO)5 
• 119850-71-4 {(C₆H₅)3P}(CO)4OsMo(CO)5 
• 119850-67-8 cis-{Phe₃P}(OC)4OsW(CO)5 
• 119850-67-8 trans-{Phe₃P}(OC)4OsW(CO)5 

Relevant academic research and scientific papers

Kinetics of Reaction of Dodecacarbonyltriosmium with Diphenylacetylene

The kinetics of reaction of Os3(CO)12 with C2Ph2 in decalin or tetradecane between 160 and 195 deg C, and under various partial pressures of CO, have been studied.Loss of Os3(CO)12 occurs by two main paths.One involves a very unusual bimolecular reaction

Multicenter transformations of the methyl ligand in CH3Os3Au carbonyl cluster complexes: Synthesis, characterization and DFT analyses

Os3(CO)11(NCCH3) and Os3(CO)10(NCCH3)2 react with (CH3)AuPPh3 to yield the new Os3Au cluster complexes, Os3(CO)10(μ-O=CCH3) (AuPPh3), 1 and Os3(CO)9(μ-η3-CH) (μ-H)2(μ-AuPPh3), 2 containing bridging acetyl and bridging methylidyne ligands, respectively, by two competing reaction pathways: 1) a methyl migration/CO insertion pathway that produces a complex with a bridging acetyl ligand. and 2) C-H bond cleavage transformations via a series of decarbonylated intermediates containing an agostically coordinated bridging methyl group, a bridging methylene group, a triply bridging methylidyne ligand and bridging hydride ligands. It has also been found that carbon monoxide can induce shifts of the bridging hydride ligands back to methylidyne ligand in 2 with subsequent cleavage of Os-Au and Os-Os bonds to yield two open cluster complexes (CH3)Os3(CO)12AuPPh3, 4 and (CH3)Os2(CO)8AuPPh3, 5 having terminally coordinated methyl ligands. The open cluster complex 4 can be converted back to 1 and 2 via decarbonylation process by using either thermal or irradiation treatments. The CO dissociation mechanisms related to the CH bond transformation processes were studied by DFT computational analyses. It has been demonstrated that the Os3Au(CH3) cluster provides a robust platform to studying multicenter C-H bond transformations and for C-C bond formation via methyl migration/CO insertion processes.

Steric limitations in associative substitution reactions of Os3(CO)9(μ-C4Ph4)

Reactions of the cluster Os3(CO)9(μ-C4Ph4) (1) with a large number of smaller P-donor nucleophiles (Tolman cone angle θ ≤ 143°) proceed rapidly in heptane at room temperature via associative adduct formation to form the monosubstituted products. However, reactions with several larger P-donor nucleophiles (θ ≤ 145°) in heptane at room temperature yield, in a single observable bimolecular step, a mixture of mononuclear and dinuclear products and it is therefore not possible to synthesize the monosubstituted clusters directly with these larger ligands. Crystallographic structures of Os3(CO)8(etpb)(μ-C4Ph 4)·(CH3OH) (2etpb) (etpb = P(OCH2)3CEt) and Os3(CO)8-(P(OPh)3)(μ-C4Ph 4)·(C6H14) (2P(OPh)3) have been determined and show that the substituent has displaced a CO ligand from the Os(CO)4 moiety in 1.

Oxygen atom transfer reactions to metal carbonyls. Kinetics and mechanism of CO substitution of M(CO)5 (M = Fe, Ru, Os) in the presence of (CH3)3NO

Reported are rates of reaction and activation parameters for CO substitution by PPh3 of M(CO)5 (M = Fe, Ru, Os) in the presence of (CH3)3NO. The reactions follow a second-order rate law, being first-order in concentrations of M(CO)5 and of (CH3)3NO but zero-order in PPh3 concentration. The reaction rates show an approximate overall fourfold increase in the order Fe Ru > Os for M3(CO)12. An attempt is made to account for the relative reaction rates of the M(CO)5 compounds and for why the order differs from that of the corresponding metal carbonyl clusters.

Wavelegth-Dependent Primary Photoprocesses of Os3(CO)12 in Fluid Solution and in Rigid Alkane Glasses at Low Temperature: Spectroscopic Detection, Characterization, and Reactivity of Coordinatively Unsaturated Os3(CO)11

Wavelegth-dependent photochemistry is reported for Os3(CO)12 in hydrocarbon solutions at 298 and 195 K and in rigid hydrocarbon glasses at 90 K.Near-UV and vis irradiation of 0.2 mM Os3(CO)12 at 298 k in alkane solutions containing 5 mM L yields mainly Os3(CO)11L (L = PPh3, P(OMe)3) as the initial photoproduct with a wavelegth-dependent quantum yield Φ436nm 366nm =0.017 +/- 0.001, and Φ313nm = 0.050 +/- 0.003 for L = PPh3, independent of the presence of added o.1 M tetrahydrofuran.Photosubstitution of PPh3 for CO is not affected by added 1 M CCl4, and the 366 nm quantum yield does not change on increasing the PPh3 concentration to 0.1 M, consistent with photodissociative loss of CO from an upper level excited state.Electronic spectral features for Os3(CO)12 become well-resolved in an alkane glass of 90 K; low-energy excitation into the first (382 nm: 10a1' -> 16e'; 1A1' -> 1E') or second (320 nm: 15e' -> 6a2'; 1A1' -> 1E') absorbtions for Os(CO)12 yields no net photochemistry in the 90 K alkane glass.However, excitation into the third electronic absorbtion (278 sh nm: 14e' -> 6a2'; 1A1' -> 1E') of 0.1 mM Os3(CO)12 yields loss of one CO as the only FTIR detected photoreaction to yield a single product, formulated as axially vacant Os3(CO)11 on the basis of FTIR and UV-vis spectral characterization and reaction chemistry.While the photogenerated Os(CO)11 reacts with 13CO at low temperature to give an axial-13CO-Os3(CO)11(13CO), UV irradiation of axial-13CO-Os3(CO)11(13CO) in a 90 K methylcyclohexane glass yields dissociative CO loss in a ratio of 12CO/13CO of greater than 28.These results suggest photodissociative loss of equatorial CO from Os3(CO)12, followed by rearrangement of equatorially vacant Os3(CO)11 to the axially vacant form.Photogenerated Os3(CO)11 reacts with two electron donor ligands to yield Os3(CO)11L complexes (L = N2,C2H4, PPh3, 1-pentene, 2-MeTHF) and with H2 to yield H2Os3(CO)11.The H2Os3(CO)11 complex has been detected by FTIR as an intermediate in the direct photoconversion (Φ366nm = 0.02) of Os3(CO)12 to H2Os3(CO)10 in H2-saturated alkane solutions at 298 K.Near-UV irradiation of H2Os3(CO)11 cleanly yields H2Os3(CO)10 and free CO at 298 or 90 K.Selective excitation into the second absorbtion of Os3(CO)12 at 90 K yields inefficient associative photosubstitution of strong ?-acceptors (C2H4, C5H10, 13CO) but not N2 or 2-MeTHF for CO.In fluid solutions, competitive photofragmentation is correlated with long wavelegth irradiation and with strong ?-acceptor ligands (CO, C2H4, not PPh3).

PHOTOCHEMICAL REACTIVITY OF Os3(CO)12 AND THERMAL ACTIVATION OF DIOSMACYCLOBUTANES TOWARDS ALKYNES

Long wavelength photolysis of Os3(CO)12 and MeO2CCCCO2Me(DMAD) in benzene gives, as isolable products, Os2(CO)8(μ-η1, η1-DMAD) (4a) and Os2(CO)6(DMAD)4 (5).Structural work confirms the diosmacyclobutene arrangement in 4a and reveals a unique coupling of alkynes in 5.The potentially more general thermal reaction between preformed diosmacyclobutane and alkynes gives improved yields of 4a and allows the isolation, albeit in low yield, of Os2(CO)8(μ-η1, η1-CF3CCCF3) (4b).

Cluster syntheses. 12. Metal-metal exchange reactions. Systematics of the synthesis of platinum-osmium carbonyl clusters containing quadruply bridging sulfido ligands

The reaction of Os5(CO)15(μ4-S) (1) heptahydrate, Pt(PPh3)2C2H4 has yielded several new platinum-osmium clusters containing quadruply bridging sulfido ligands and Os5(CO)14(PPh3)(μ4-S) (3). The three platinum-osmium clusters PtOs4(CO)13(PPh3)(μ4-S) (2), PtOs5(CO)15(PPh3)(μ4-S) (4), and PtOs5(CO)15(PPh3)2(μ 4-S) (6) have been characterized by single-crystal X-ray diffraction analyses. For 2: space group P1, a = 13.116 (4) A?, b = 9.655 (3) A?, c = 14.669 (4) A?, α = 89.68 (3)°, β = 104.79 (2)°, γ = 89.11 (3)°, Z = 2, ρcalcd = 2.99 g/cm3. The structure was solved by the heavy-atom method and refined (4505 reflections) to the final residuals RF = 0.044 and RwF = 0.052. The molecule consists of a square-pyramidal cluster of four osmium atoms and one platinum atom with a quadruply bridging sulfido ligand on the square base. The platinum atom lies in the square base. For 4: space group P21/c, a = 8.986 (7) A?, b = 16.605 (5) A?, c = 26.005 (8) A?, β = 97.62 (4)°, Z = 4, ρcalcd = 3.21 g/cm3. The structure of 4 was solved by direct methods and was refined (3947 reflections) to the final residuals RF = 0.040 and ground = 0.048. The molecule consists of a square-pyramidal cluster of five osmium atoms with a quadruply bridging sulfido ligand on the square base and a Pt(CO)PPh3 moiety bridging one of the triosmium triangles. For 6: space group P1, a = 12.538 (2) A?, b = 15.908 (2) A?, c = 18.061 (2) A?, α = 63.008 (9)°, β = 76.629 (9)°, γ = 65.68 (1)°, Z = 2, ρcalcd = 2.45 g/cm3. The structure was solved by the heavy-atom method and was refined (4976 reflections) to the final residuals RF = 0.049 and RwF = 0.065. The molecule consists of a square-pyramidal cluster of four osmium atoms and one platinum atom with the base bridged by a quadruply bridging sulfido ligand and one of the osmium-osmium bonds in the square base bridged by an Os(CO)3(PPh3) moiety. Compound 6 is believed to be an intermediate in the formation of 2. 6 reacts with carbon monoxide to yield both 2 and 3. The yield of 6 is increased when the reaction is performed in the presence of PPh3. The yield of 4 is increased when the reaction is performed under CO. A scheme based on hexanuclear intermediates is proposed to explain the formation of all the products.

Substitution and fragmentation reactions of Br2Os3(CO)12 with phosphines. Structure of Br2Os3(CO)10[P(OMe)3]2

At room temperature the linear complex Br2Os3(CO)12 reacts with PPh3 and PPh2Me to give the substituted product Br2Os3(CO)10(PR3)2 (?15%), as well as the mononuclear products Os(CO)4PR3 (?60%) and Br2Os(CO)2(PR3)2 (?15%). The mononudear products are not formed from Br2Os3(CO)10(PR3)2 under the conditions of the reaction. The reaction is completely stopped by added CCl4 or galvinoxyl, suggesting that the formations of both the trinuclear and mononuclear products are radical processes. From the reaction of Br2Os3(CO)12 with P(OMe)3, the trinuclear complex Br2Os3(CO)10[P(OMe)3]2 is isolated in 53% yield. This complex crystallizes in the centrosymmetric triclinic space group P1 with a = 8.923 (3) ?, b = 11.657 (3) ?, c = 8.185 (3) ?, α = 98.48 (3)°, β = 111.91 (3)°, γ = 96.28 (3)°, and Z = 1; it has the structure.