Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2

V. A. Maksakov, I. V. Slovohotova, A. V. Golovin, S. P. Babailov

Research output: Contribution to journal › Article

Abstract

The reactions of the heterometallic complexes (μ-H)Os₃(μ-O₂CC₅H₄FeCp)(CO)₁₀ (1) and Fe{(μ-O₂CC₅H₄)(μ-H)Os₃(CO)₁₀}₂ (2) with CF₃COOH, CF₃SO₃H, and AcCI were studied. The reaction of 1 with CF₃COOH involves interaction with the Cp ligands, protonation of the O atom of the bridging carboxylate group, and oxidative degradation of the complex. At low concentrations, CF₃SO₃H protonates the O atom of the bridging carboxylate group, while at high concentrations, degradation of the complex takes place. The reaction of complex 2 with either CF₃COOH or low concentrations of CF₃SO₃H results in successive elimination of two [(μ-H)Os₃(CO)₁₀] cluster fragments due to protonation of the O atoms of the carboxylate groups. In the case of high CF₃SO₃H concentrations, the Os-Os bonds of both cluster fragments of 2 are also protonated to give the [Fe{(μ-O₂CC₅H₄)(μ-H)₂Os₃(CO)₁₀}₂]²⁺ dication. The Friedel-Crafts acylation of 1 takes place only when a large excess of AcCl and AlCl₃ is used to give two new complexes, (μ-H)Os₃(μ-O₂CC₅H₄FeC₅H₄C(O)CH₃)(CO)₁₀ and (μ-H)Os₃(μ-O₂CC₅H₃C(O)CH₃FeCp)(CO)₁₀ in a 2 : 1 ratio.

Original language	English
Pages (from-to)	2451-2458
Number of pages	8
Journal	Russian Chemical Bulletin
Volume	50
Issue number	12
DOIs	https://doi.org/10.1023/A:1015064419785
Publication status	Published - Dec 2001
Externally published	Yes

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Acylation

Protonation

Carbon Monoxide

Atoms

Degradation

Ligands

Keywords

H NMR spectroscopy
Acylation
Osmium and iron heterometallic complexes
Protonation

ASJC Scopus subject areas

Chemistry(all)

Cite this

Maksakov, V. A., Slovohotova, I. V., Golovin, A. V., & Babailov, S. P. (2001). Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2. Russian Chemical Bulletin, 50(12), 2451-2458. https://doi.org/10.1023/A:1015064419785

Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2. / Maksakov, V. A.; Slovohotova, I. V.; Golovin, A. V.; Babailov, S. P.

In: Russian Chemical Bulletin, Vol. 50, No. 12, 12.2001, p. 2451-2458.

Research output: Contribution to journal › Article

Maksakov, VA, Slovohotova, IV, Golovin, AV & Babailov, SP 2001, 'Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2', Russian Chemical Bulletin, vol. 50, no. 12, pp. 2451-2458. https://doi.org/10.1023/A:1015064419785

Maksakov VA, Slovohotova IV, Golovin AV, Babailov SP. Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2. Russian Chemical Bulletin. 2001 Dec;50(12):2451-2458. https://doi.org/10.1023/A:1015064419785

Maksakov, V. A. ; Slovohotova, I. V. ; Golovin, A. V. ; Babailov, S. P. / Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2. In: Russian Chemical Bulletin. 2001 ; Vol. 50, No. 12. pp. 2451-2458.

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title = "Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2",

abstract = "The reactions of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 (1) and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2 (2) with CF3COOH, CF3SO3H, and AcCI were studied. The reaction of 1 with CF3COOH involves interaction with the Cp ligands, protonation of the O atom of the bridging carboxylate group, and oxidative degradation of the complex. At low concentrations, CF3SO3H protonates the O atom of the bridging carboxylate group, while at high concentrations, degradation of the complex takes place. The reaction of complex 2 with either CF3COOH or low concentrations of CF3SO3H results in successive elimination of two [(μ-H)Os3(CO)10] cluster fragments due to protonation of the O atoms of the carboxylate groups. In the case of high CF3SO3H concentrations, the Os-Os bonds of both cluster fragments of 2 are also protonated to give the [Fe{(μ-O2CC5H4)(μ-H)2Os3(CO)10}2]2+ dication. The Friedel-Crafts acylation of 1 takes place only when a large excess of AcCl and AlCl3 is used to give two new complexes, (μ-H)Os3(μ-O2CC5H4FeC5H4C(O)CH3)(CO)10 and (μ-H)Os3(μ-O2CC5H3C(O)CH3 FeCp)(CO)10 in a 2 : 1 ratio.",

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T1 - Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2

AU - Maksakov, V. A.

AU - Slovohotova, I. V.

AU - Golovin, A. V.

AU - Babailov, S. P.

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N2 - The reactions of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 (1) and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2 (2) with CF3COOH, CF3SO3H, and AcCI were studied. The reaction of 1 with CF3COOH involves interaction with the Cp ligands, protonation of the O atom of the bridging carboxylate group, and oxidative degradation of the complex. At low concentrations, CF3SO3H protonates the O atom of the bridging carboxylate group, while at high concentrations, degradation of the complex takes place. The reaction of complex 2 with either CF3COOH or low concentrations of CF3SO3H results in successive elimination of two [(μ-H)Os3(CO)10] cluster fragments due to protonation of the O atoms of the carboxylate groups. In the case of high CF3SO3H concentrations, the Os-Os bonds of both cluster fragments of 2 are also protonated to give the [Fe{(μ-O2CC5H4)(μ-H)2Os3(CO)10}2]2+ dication. The Friedel-Crafts acylation of 1 takes place only when a large excess of AcCl and AlCl3 is used to give two new complexes, (μ-H)Os3(μ-O2CC5H4FeC5H4C(O)CH3)(CO)10 and (μ-H)Os3(μ-O2CC5H3C(O)CH3 FeCp)(CO)10 in a 2 : 1 ratio.

AB - The reactions of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 (1) and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2 (2) with CF3COOH, CF3SO3H, and AcCI were studied. The reaction of 1 with CF3COOH involves interaction with the Cp ligands, protonation of the O atom of the bridging carboxylate group, and oxidative degradation of the complex. At low concentrations, CF3SO3H protonates the O atom of the bridging carboxylate group, while at high concentrations, degradation of the complex takes place. The reaction of complex 2 with either CF3COOH or low concentrations of CF3SO3H results in successive elimination of two [(μ-H)Os3(CO)10] cluster fragments due to protonation of the O atoms of the carboxylate groups. In the case of high CF3SO3H concentrations, the Os-Os bonds of both cluster fragments of 2 are also protonated to give the [Fe{(μ-O2CC5H4)(μ-H)2Os3(CO)10}2]2+ dication. The Friedel-Crafts acylation of 1 takes place only when a large excess of AcCl and AlCl3 is used to give two new complexes, (μ-H)Os3(μ-O2CC5H4FeC5H4C(O)CH3)(CO)10 and (μ-H)Os3(μ-O2CC5H3C(O)CH3 FeCp)(CO)10 in a 2 : 1 ratio.

KW - H NMR spectroscopy

KW - Acylation

KW - Osmium and iron heterometallic complexes

KW - Protonation

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10.1023/A:1015064419785