Triphenylphosphine-substituted selenido and sulfido clusters of osmium derived from Ph3PSe or Ph3PS

Akter, Hamida; Deeming, Antony J.; Kabir, Shariff E.; Mondol, Dwijendro N.; Nordlander, Ebbe; Sharmin, Ayesha; Tocher, Derek A.

doi:10.1016/j.jorganchem.2005.07.038

Cited by 12 publications

(5 citation statements)

References 41 publications

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“…In addition to the phenyl proton resonances in the aromatic region, the 1 H NMR spectrum shows two multiplets at δ 4.80 and 4.22 assigned to the cyclopentadienyl protons and a triplet at δ −0.68 ( J P - H = 3.4 Hz) due to the hydroxide bridges. The latter is typical and compares well with that of other structurally characterized hydroxyl-bridged trimetallic complexes: [Ru 3 (CO) 8 (μ-BINAP)(μ-OH) 2 ] [δ −1.48, J P - H = 4.0 Hz], [Os 3 (CO) 8 (μ-dppm)(μ-OH)(μ-H)] [δ −0.44, J P - H = 4.3 Hz], and [Os 3 (CO) 8 (PPh 3 ) 2 (μ-OH) 2 (μ-H)] [δ −0.18, J P - H = 3.6 Hz] . The 31 P{ 1 H} NMR spectrum shows a singlet at δ 2.4, indicating the equivalence of the phosphorus atoms.…”

Section: Resultssupporting

confidence: 75%

Chelate and Bridge Diphosphine Isomerization: Triosmium and Triruthenium Clusters Containing 1,1‘-Bis(diphenylphosphino)ferrocene (dppf)

et al. 2007

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The coordination mode of dppf {dppf ) 1,1′-bis(diphenylphosphino)ferrocene} at triosmium and triruthenium carbonyl clusters has been studied. Heating [Os 3 (CO) 12 ] with dppf in the presence of Me 3 -NO in benzene at 60 °C furnishes three triosmium compounds, [Os 3 (CO) 11 (κ 1 -dppf)] (1), [Os 3 (CO) 10 -(κ 2 -dppf)] (2), and [Os 3 (CO) 10 (µ-dppf)] (3) in 10, 20, and 30% yields, respectively. Reaction of the labile cluster [Os 3 (CO) 10 (MeCN) 2 ] with dppf at room temperature also gives 1, 2, and 3 (5, 10, and 35% yields). Treatment of 1, which contains a pendant diphosphine, with Me 3 NO at room temperature affords 2 via a ring closure reaction, whereas heating 2, in which the dppf ligand is chelating, at 110 °C affords the thermodynamically stable bridging isomer 3, in which phosphorus atoms are bound at equatorial positions. Reaction of the unsaturated cluster [Os 3 (CO) 10 (µ-H) 2 ] (4) with dppf in refluxing THF affords the bridging complex [Os 3 (CO) 8 (µ-dppf)(µ-H) 2 ] (6) in high yield as the sole product. Hydrogenation of 3 with H 2 at 110 °C at 1 atm also yields 6. Reactions of both the saturated [Os 3 (CO) 10 (µ-dppm)] ( 7) and electrondeficient [Os 3 (CO) 8 {µ 3 -Ph 2 PCH 2 P(Ph)C 6 H 4 }(µ-H)] (8) with dppf at 110 °C and at room temperature respectively yield [Os 3 (CO) 9 (µ-dppm)(κ 1 -dppf)] ( 9) and [Os 3 (CO) 8 (µ-dppm)(κ 2 -dppf)] (10). Compound 9 converts to 10 at 110 °C via CO loss and phosphorus coordination. Reaction of [Ru 3 (CO) 12 ] with dppf in the presence of Me 3 NO affords the dihydroxy-bridged complex, [Ru 3 (CO) 8 (µ-dppf)(µ-OH) 2 ] (13), together with the previously reported compounds [Ru 3 (CO) 10 (µ-dppf)] ( 11) and [Ru 3 (CO) 8 (µ-dppf) 2 ] (12).

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Section: Resultssupporting

confidence: 75%

Chelate and Bridge Diphosphine Isomerization: Triosmium and Triruthenium Clusters Containing 1,1‘-Bis(diphenylphosphino)ferrocene (dppf)

et al. 2007

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“…The shortness of the nonbonding Os(1)/ Os(3) distance in 2 can be attributed to the presence of the two bridging ligands that bridge these two metal atoms using only one atom. Compound 2 is similar to the compounds Os 3 (CO) 10 (m-OMe) 2 , 4 [14] and Os 3 (CO) 8 (PPh 3 ) 2 (m-OH) 2 [18] for which the distance between the two nonbonded osmium atoms is 3.078(3) Å and 3.1197(2) Å, respectively.…”

Section: Ph 3 Snmentioning

confidence: 74%

Complexes containing bridging tin- and germanium-substituted metallocarboxylate ligands from the reactions of Ph3SnOH and Ph3GeOH with Os3(CO)12 in the presence of base

Adams

Chen

Trufan

2011

Journal of Organometallic Chemistry

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“…Chalcogenide-bridged derivatives of transition metal carbonyl clusters have been widely studied. [1][2][3][4][5][6][7] Examples of such compounds include the triruthenium hydrido clusters [(µ-H) 2 Ru 3 (µ 3 -E)(CO) 9-2x (dppm) x ] (E = O, x = 2; E = S, x = 1, 2), which have been shown to be efficient catalyst precursors for olefin hydrogenation reactions. 7,8 In these clusters, the triply bridging chalcogenide ligands may function as "clamps" that maintain an intact cluster framework throughout reactions.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl clusters – diastereomeric control of enantioselectivity

et al. 2020

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Triphenylphosphine-substituted selenido and sulfido clusters of osmium derived from Ph3PSe or Ph3PS

Cited by 12 publications

References 41 publications

Chelate and Bridge Diphosphine Isomerization: Triosmium and Triruthenium Clusters Containing 1,1‘-Bis(diphenylphosphino)ferrocene (dppf)

Chelate and Bridge Diphosphine Isomerization: Triosmium and Triruthenium Clusters Containing 1,1‘-Bis(diphenylphosphino)ferrocene (dppf)

Complexes containing bridging tin- and germanium-substituted metallocarboxylate ligands from the reactions of Ph3SnOH and Ph3GeOH with Os3(CO)12 in the presence of base

Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl clusters – diastereomeric control of enantioselectivity

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