72282-41-8Relevant academic research and scientific papers
Triphenylphosphine-substituted selenido and sulfido clusters of osmium derived from Ph3PSe or Ph3PS
Akter, Hamida,Deeming, Antony J.,Golzar Hossain,Kabir, Shariff E.,Mondol, Dwijendro N.,Nordlander, Ebbe,Sharmin, Ayesha,Tocher, Derek A.
, p. 4628 - 4639 (2007/10/03)
Cleavage of PSe bonds occurs readily in the room-temperature treatment of [Os3(CO)10(MeCN)2] with Ph3PSe to give three new compounds, [Os3(μ3-Se) 2(CO)8(PPh3)] (2), [Os3(μ 3-Se)(μ3-CO)(CO)7(PPh3) 2] (5) and [Os3(μ-OH)2(CO) 8(PPh3)2] (6), respectively, and three known compounds, [Os3(μ3-Se)2(CO)9] (1), [Os3(μ3-Se)(μ-CO)2(CO) 7(PPh3)] (3), and 1,2-[Os3(CO) 10(PPh3)2] (4).No evidence for any product containing a co-ordinated Ph3PSe ligand was obtained.The analogous reaction between [Os3(CO)10(MeCN)2] and Ph 3PS produces five new compounds [Os3(μ3-S) 2(CO)8(PPh3)] (7), [Os3(μ 3-S)(μ-CO)2(CO)7(PPh3)] (8), [Os3(μ3-S)(μ3- CO)(CO) 7(PPh3)2] (9), [Os3(μ 3-)2(CO)7(PPh3)2] (11) and compound 6 in addition to the known compound 4. Treatment of 2 with Me 3NO at 50 °C gives the trinuclear cluster [Os3(μ 3-Se)2(CO)7(PPh3)(NMe3)] (13) and the hexanuclear cluster [Os6(μ3-Se) 4(CO)14(PPh3)2] (12). Treatment of compound 1 with PPh3 and Me3NO at room temperature gives [Os3(μ3-Se)2(CO)7(PPh 3)2] (10). Compound 2 reacts with PPh3 similarly to give 10. Compound 3 reacts with elemental selenium at 110 °C to give 2. The new compounds 2, 5, 6 and 8 were characterized by single-crystal X-ray diffraction. The compounds 3, 5, 8 and 9 contain Os3(μ 3-S) or Os3(μ3-Se)cluster cores with three metal-metal bonds while 2, 7, 10, 11 and 12 contain Os3(μ 3-S)2or Os3(μ3-Se)2 cores two metal-metal bonds. The two hydroxy ligands in the triosmium cluster 6 bridging the open osmium-osmium edge and are probably derived from water. A study of the dynamic exchange of PPh3 ligands in 5 is also reported.
The reaction of triphenylphosphine selenide with triosmium clusters: a facile cluster coupling through a selenium atom
Leong, Weng Kee,Leong, Wei Lin Janet,Zhang, Junlian
, p. 1087 - 1090 (2007/10/03)
The room temperature reactions of Ph3PSe with the triosmium clusters Os3(CO)11(CH3CN), Os3(CO)10(CH3CN)2 and Os3(μ-H)2(CO)10 have been investigated. The reaction with an equimolar amount of Os3(CO)11(CH3CN) afforded the known clusters Os3(μ3-Se)2(CO)9, 1, and Os3(CO)11(PPh3), 2, and the new cluster Os3(μ3-Se)(CO)9(PPh3), 3. The analogous reaction with Os3(CO)10(CH3CN)2 gave 1 and 2; reaction with 0.5 equivalent of the cluster gave 1 quantitatively. The reaction with Os3(μ-H)2(CO)10 gave two new clusters, viz. Os3(μ3-Se)(μ-H)2(CO)8(PPh3), 4a, and Os6(μ3-Se)(H)(μ-H)3(CO)18(PPh3)2, 5a. Single crystal structures of 3, 4a and 5a have been obtained. Cluster 3 possesses bridging carbonyls; these appear to have been lost on elongation of the osmium-osmium bonds by bridging hydrides in 4a. The structure of 5a is novel and comprises a naked μ3-Se atom bridging two triosmium moieties; an Os3(μ-H0(CO)10 unit and an Os3(H)(μ-H)2(CO)8(PPh3)2 unit.
Selenido osmium carbonyl cluster compounds. Structure, bonding, and reactivity of the electron-rich cluster Os4(CO)12(μ3-Se)2
Adams, Richard D.,Horváth, István T.
, p. 4718 - 4722 (2008/10/08)
The compound HOs3(CO)10(μ-SePh) (3) has been prepared (75% yield) by the reaction of Os3(CO)10(NCMe)2 with PhSeH. Under the conditions 160°C (3000 psi CO), 3 eliminates benzene and is transformed into the compounds Os3(CO)9(μ3-Se)2 (4) and Os(CO)5 in 95% yield. When irradiated (UV) under an atmosphere of CO, 3 loses benzene and is converted to Os3(CO)9(μ3-CO)(μ3-Se) (5) in 18% yield. When irradiated in the presence of Os(CO)5, 4 adds one Os(CO)4 moiety to form the compound Os4(CO)13(μ3-Se)2 (6) in 33% yield. At 125°C, 6 loses 1 mol of CO to form the cluster Os4(CO)12(μ3-Se)2 (7) quantitatively. 7 has been characterized by a single-crystal X-ray diffraction analysis: space group P1 (No. 2), a = 13.987 (4) A?, b = 16.371 (6) A?, c = 9.491 (6) A?, α = 106.04 (4)°, β = 90.31 (4)°, γ = 81.63 (3)°, V = 2065 (3) A?3, Z = 4, ρcalcd = 4.036 g/cm3. The structure was solved by direct methods and refined (4036 reflections, F2 ≥ 3.0σ(F2)) to the final residuals RF = 0.047 and RwF = 0.056. The molecule consists of a butterfly tetrahedral cluster of four osmium atoms, with triply bridging selenido ligands bridging the two open triangular faces. The metal-metal bonding is irregular, with two of the five metal-metal bonds being greater than 3.00 A? in length. 7 adds 1 mol of CO under mild conditions (25°C (1 atm CO)) to re-form 6 quantitatively. At 125°C, 7 oxidatively adds 1 mol of H2 to yield the compound H2Os4(CO)12(μ3-Se)2 (8) in 35% yield. 5 reacts with H2 at 125°C to form H2Os3(CO)9(μ3-Se) (9) in 39% yield.
