16406-49-8Relevant academic research and scientific papers
Facile cycloreversion of octacarbonyl-1,2-diosmacyclobutane: Convenient source of the Os2(CO)8 unit in the formation of 1,2-diosmacyclobutenes
Burke, Michael R.,Seils, Frank,Takats, Josef
, p. 1445 - 1450 (2008/10/08)
Cycloreversion of octacarbonyl-1,2-diosmacyclobutane, Os2(CO)8(μ-η1:η1-CH 2CH2) (1), can be affected by mild thermal (T > 28°C) or photochemical (λ > 330 nm) activation. In the presence of activated alkynes the reaction affords 1,2-diosmacyclobutenes in moderate to good yields, Os2(CO)8(μ-η1:η 1-RCCR′) (R = R′ = CO2Me (2a), Ph (2b); R = H, R′ = CO2Me (2c), C(O)Me (2d)). Compounds 2 have been characterized by IR and NMR spectroscopies. The 13C NMR spectra indicate that the molecules are static at room temperature with regard to CO exchange processes. A detailed preparation of 1 is reported as well.
Kinetics of Reaction of Dodecacarbonyltriosmium with Diphenylacetylene
Poe, Anthony J.,Sampson, Clifford N.,Smith, Richard T.
, p. 5459 - 5464 (2007/10/02)
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
Metal-induced cleavage of carbon-sulfur bonds in thiolato ligands. Thermolysis of HOs3(CO)10(μ-SC6H5) under CO pressure. The synthesis and crystal and molecular structures off Os4(CO)13(μ3-S) and Os5(CO)15(μ4-S)
Adams, Richard D.,Horvàth, Istvàn T.,Segmüller, Brigitte E.,Yang, Li-Wu
, p. 1301 - 1308 (2008/10/08)
The thermolysis of HOs3(CO)10(μ-SC6H5), I, has been studied under carbon monoxide pressures of 200 and 1800 psi at 150°C. At 200 psi, I eliminates C6H6 and forms the new compounds Os4(CO)13(μ3-S), II, and Os5(CO)15(μ4-S), III, and the known compounds Os3(CO)9(μ3-S)2, IV, and Os3(CO)12. Compounds II and III have been characterized by X-ray crystallographic methods. For II: space group P1, No. 2, a = 9.608 (2) A?, b = 15.402 (2) A?, c = 15.703 (3) A?, α = 113.29 (2)°, β = 99.04 (2)°, γ = 95.52 (2)°, V = 2077 (2) A?3, Z = 4, ρcalcd = 3.70 g/cm3. The structure was solved by the heavy-atom method. For 3998 reflections (F2 ≥ 3.0σ(F2)) RF = 0.040 and RwF = 0.046. The structure consists of a butterfly cluster of four osmium atoms with a triply bridging sulfido ligand on one triangular group of three. There are 13 linear terminal carbonyl ligands. When heated in the absence of CO, II loses 1 mol of CO and forms the Os4(CO)12(μ3-S) which contains a closed tetrahedron of four metal atoms. For III: space group Pna21, No. 33, a = 19.119 (4) A?, b = 7.724 (6) A?, c = 16.417 (4) A?, V = 2424 (3) A?3, Z = 4, ρcalcd = 3.84 g/cm3. The structure was solved by direct methods. For 1520 reflections (F2 ≥ 3.0σ(F2)) RF = 0.037 and RwF = 0.042. The structure consists of a square-pyramidal cluster of five osmium atoms with a quadruply bridging sulfido ligand spanning the square base. Each metal atom contains three linear terminal carbonyl ligands. At 1800 psi of CO pressure thermolysis of I yields C6H6, Os3(CO)9(μ3-S)2, and Os(CO)5 only. A reaction mechanism involving Os3-(CO)9(μ3-S) and Os(CO)4 intermediates is proposed and discussed.
A High-pressure Infrared Study of the Stability of Some Ruthenium and Osmium Clusters to CO and H2 under Pressure
Nicholls, J. Nicola,Farrar, David H.,Jackson, Peter F.,Johnson, Brian F. G.,Lewis, Jack
, p. 1395 - 1400 (2007/10/02)
A high-pressure i.r. study has been made of the stability of some high-nuclearity carbonyl clusters of ruthenium and osmium to carbon monoxide and hydrogen, and of the thermal stabilities of theses clusters under an inert atmosphere.In solution, the hexanuclear cluster reacts with CO (90 atm, 160 deg C, 1 h) to produce the new pentanuclear cluster and .In contrast, in the solid state adds 2 mol of CO to form .The pentanuclear carbonyl undergoes reaction with CO to give both and , and with to give .On heating in an inert atmosphere loses CO to generate .This reaction is reversible.Reaction of , , , or with H2 under moderate pressure and temperatures gives and OsH2(CO)4>; first produces and proceeds to the same pruducts.On carbonylation under pressure yields , and gives a mixture of and .Pyrolysis of under argon at 120 deg C gives the hexanuclear carbide in high yield.
