TY - JOUR
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.
PY - 2001/12
Y1 - 2001/12
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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U2 - 10.1023/A:1015064419785
DO - 10.1023/A:1015064419785
M3 - Article
AN - SCOPUS:0035740674
VL - 50
SP - 2451
EP - 2458
JO - Russian Chemical Bulletin
JF - Russian Chemical Bulletin
SN - 1066-5285
IS - 12
ER -