Oxyligand derivatives of triosmium dodecacarbonyl

Frauenhoff, Greg R.

doi:10.1016/0010-8545(92)80066-z

Cited by 14 publications

(5 citation statements)

References 65 publications

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“…The easy activation of a rather unreactive molecule such as [Os 3 (CO) 12 ] is still a difficult task, when total high yields are required. Much work has been devoted to the synthesis of clusters of the type [HOs 3 (CO) 10 Y] [Os 3 (CO) 10 (cyclohexa-1,3-diene)], [Os 3 (CO) 10 (cyclooctene) 2 ], and [HOs 3 (CO) 10 (NCHNMe 2 )] 8 have been synthesized but in 60−76% yields only, starting from [H 2 Os 3 (CO) 10 ], prepared by hydrogenation of [Os 3 (CO) 12 ] (73% yield) .…”

Section: Introductionmentioning

confidence: 99%

Surface-Mediated Organometallic Synthesis: The Activating Role of Silica for a High-Yield Route to [H₄Os₄(CO)₁₂] and [HOs₃(CO)₁₀Y] (Y = OH, OR, Cl, Br, I, O₂CR, SCN) Clusters from [Os₃(CO)₁₂]

et al. 1997

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Activation of [Os3(CO)12] by the silica surface via reaction with surface silanol groups provides a new convenient general approach to the selective, high-yield synthesis of various osmium carbonyl clusters such as [H4Os4(CO)12] and [HOs3(CO)10Y] (Y = a three-electron donor such as OH, OR, Cl, Br, I, O2CR, and SCN). These silica-mediated syntheses compare favorably with the more conventional syntheses in solution because (i) differently from other related intermediates used in solution, silica-anchored [HOs3(CO)10(OSi⋮)] is easily obtained in quantitative yield starting from [Os3(CO)12] in one step and (ii) the conversion of [HOs3(CO)10(OSi⋮)] occurs in one pot usually in high yields and under mild reaction conditions. In addition, the related species [HOs3(CO)10(OH)], which can be obtained almost quantitatively by hydrolysis of [HOs3(CO)10(OSi⋮)], is even more reactive than its precursor and allows a three-step synthesis of various osmium clusters characterized by excellent total yields from [Os3(CO)12].

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Section: Introductionmentioning

confidence: 99%

Surface-Mediated Organometallic Synthesis: The Activating Role of Silica for a High-Yield Route to [H₄Os₄(CO)₁₂] and [HOs₃(CO)₁₀Y] (Y = OH, OR, Cl, Br, I, O₂CR, SCN) Clusters from [Os₃(CO)₁₂]

et al. 1997

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“…The electrospray ionisation mass spectrometry in the positive mode showed peaks corresponding to [M] + (for 3b-e and 3g-h) or fragments due to loss of carbonyl ligands (for 3a, 3f and 3i-j) have been assigned unambiguously on the basis of the characteristic triosmium isotopic pattern. The room temperature 1 H NMR spectra displayed resonances attributable to the respective organic chalcone or benzaldehyde moiety, and a single hydride resonance (δ -10 ppm) which is characteristic for carboxylato-bridged triosmium clusters [11].…”

Section: Resultsmentioning

confidence: 99%

“…Ten terminal carbonyl ligands, three on each of the two bridged osmium atoms and four on the remaining osmium atom, complete the ligand shell. The σ-donating and weak π-accepting properties of the carboxylato ligand results in more electron density being donated from Os(1) and Os (2) to the corresponding trans carbonyls, CO (11) and CO (21), respectively. This is manifested in the Os(1)−C (13) and Os(2 1.279( 12) 1.266( 13) 1.259( 8)…”

Section: Methodsmentioning

confidence: 99%

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Carboxylated Chalcone and Benzaldehyde Derivatives of Triosmium Carbonyl Clusters: Synthesis, Characterization and Biological Activity Towards MCF-7 Cells

et al. 2019

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“…Complex 3 is found to be the intermediate of this reaction. We propose that the transformation of 3 to 8 proceeds by the insertion of hydride into the N−O bond of the complexed ligand . This results in the formation of a terminal Os−OH intermediate that possesses a tendency to undergo migration into the Os−Os metal bond, thereby forming a bridging μ-η 1 -OH moiety …”

Section: Discussionmentioning

confidence: 99%

Reactions of 1-Hydroxypyridine-2-thione with Triosmium Clusters. Preparation and Transformation of N-Oxide-Containing Osmium Complexes

et al. 1996

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The reaction of 1-hydroxypyridine-2-thione with Os3(CO)11(NCMe) has yielded three new complexes Os3(CO)10(μ-H)(μ-η1-S-C5H4N(O)) (1, 11% yield), Os3(CO)10(μ-H)(η2-S-C5H4N(O)) (2, 16% yield), and Os3(CO)9(μ-H)(μ-η2:η1-SC5H4N(O)) (3, 3% yield). Similarly, treatment of complex Os3(CO)10(NCMe)2 with this ligand has produced the major complexes 1 and trace of 3. Prolonging the above two reactions increased the yield of 3. Treatment of 1-hydroxypyridine-2-thione with triosmium isocyanide complexes Os3(CO)10(CNR)(NCMe) (a, R = CH2Ph; b, R = Pr) has led to the formation of Os3(CO)9(μ-H)(CNR)(η2-SC5H4N(O)) (4), Os3(CO)10(μ-η1-CNHCH2Ph)(μ-η1-S-C5H4N(O)) (5), and Os3(CO)9(μ-H)(CNR)(μ-η1-S-C5H4N(O)) (6). The 4:5 ratio depended upon the nature of the alkyl groups of the coordinated isocyanide. Reaction of either 1 or 2 with Me3NO resulted in CO loss and formation of complex 3. Thermolysis of 1 at 80 °C generated Os3(CO)9(μ-H)(μ3-pyS) (7), Os3(CO)9(μ-OH)(μ3-pyS) (8), and byproduct CO2. Upon being heated at 80 °C, 3 was converted to 7 and 8 in a ratio of 1:4 as indicated by an in-situ NMR study. These observations show that 3 is an intermediate for the formation of 8 from 1. Crystal structures of 1, 4b, 5a, and 8 were determined by X-ray diffraction analyses. The overall results indicate that the N-oxide group in these complexes exhibits versatile bonding modes on triosmium clusters.

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Oxyligand derivatives of triosmium dodecacarbonyl

Cited by 14 publications

References 65 publications

Surface-Mediated Organometallic Synthesis: The Activating Role of Silica for a High-Yield Route to [H₄Os₄(CO)₁₂] and [HOs₃(CO)₁₀Y] (Y = OH, OR, Cl, Br, I, O₂CR, SCN) Clusters from [Os₃(CO)₁₂]

Surface-Mediated Organometallic Synthesis: The Activating Role of Silica for a High-Yield Route to [H₄Os₄(CO)₁₂] and [HOs₃(CO)₁₀Y] (Y = OH, OR, Cl, Br, I, O₂CR, SCN) Clusters from [Os₃(CO)₁₂]

Carboxylated Chalcone and Benzaldehyde Derivatives of Triosmium Carbonyl Clusters: Synthesis, Characterization and Biological Activity Towards MCF-7 Cells

Reactions of 1-Hydroxypyridine-2-thione with Triosmium Clusters. Preparation and Transformation of N-Oxide-Containing Osmium Complexes

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Oxyligand derivatives of triosmium dodecacarbonyl

Cited by 14 publications

References 65 publications

Surface-Mediated Organometallic Synthesis: The Activating Role of Silica for a High-Yield Route to [H4Os4(CO)12] and [HOs3(CO)10Y] (Y = OH, OR, Cl, Br, I, O2CR, SCN) Clusters from [Os3(CO)12]

Surface-Mediated Organometallic Synthesis: The Activating Role of Silica for a High-Yield Route to [H4Os4(CO)12] and [HOs3(CO)10Y] (Y = OH, OR, Cl, Br, I, O2CR, SCN) Clusters from [Os3(CO)12]

Carboxylated Chalcone and Benzaldehyde Derivatives of Triosmium Carbonyl Clusters: Synthesis, Characterization and Biological Activity Towards MCF-7 Cells

Reactions of 1-Hydroxypyridine-2-thione with Triosmium Clusters. Preparation and Transformation of N-Oxide-Containing Osmium Complexes

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Product

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Surface-Mediated Organometallic Synthesis: The Activating Role of Silica for a High-Yield Route to [H₄Os₄(CO)₁₂] and [HOs₃(CO)₁₀Y] (Y = OH, OR, Cl, Br, I, O₂CR, SCN) Clusters from [Os₃(CO)₁₂]

Surface-Mediated Organometallic Synthesis: The Activating Role of Silica for a High-Yield Route to [H₄Os₄(CO)₁₂] and [HOs₃(CO)₁₀Y] (Y = OH, OR, Cl, Br, I, O₂CR, SCN) Clusters from [Os₃(CO)₁₂]