Trifluoroacetylacetonate rhodium(III) methyl complexes, cis-[Rh(TFA)(PPh3)2(CH3)(L)][BPh4] and cis-[Rh(TFA)(PPh3)2(CH3)(I)] (L = CH3CN, NH3, pyridine), in comparison with their acetylacetonate analogs |
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| Authors: | Elizaveta P Shestakova Viktor N Khrustalev Ivan S Podkorytov Aleksei B Nikolskii |
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| Institution: | a St. Petersburg State University, Petrodvorets, Universitetskii Pr., 26, 198504 St. Petersburg, Russian Federation
b Nesmeyanov Institute of Organoelement Compounds, Vavilova Str., 28, 117813 Moscow, Russian Federation |
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| Abstract: | The oxidative addition of CH3I to planar rhodium(I) complex Rh(TFA)(PPh3)2] in acetonitrile (TFA is trifluoroacetylacetonate) leads to the formation of cationic, cis-Rh(TFA)(PPh3)2(CH3)(CH3CN)]BPh4] (1), or neutral, cis-Rh(TFA)(PPh3)2(CH3)(I)] (4), rhodium(III) methyl complexes depending on the reaction conditions. 1 reacts readily with NH3 and pyridine to form cationic complexes, cis-Rh(TFA)(PPh3)2(CH3)(NH3)]BPh4] (2) and cis-Rh(TFA)(PPh3)2(CH3)(Py)]BPh4] (3), respectively. Acetylacetonate methyl complex of rhodium(III), cis-Rh(Acac)(PPh3)2(CH3)(I)] (5), was obtained by the action of NaI on cis-Rh(Acac)(PPh3)2(CH3)(CH3CN)]BPh4] in acetone at −15 °C. Complexes 1-5 were characterized by elemental analysis, 31P{1H}, 1H and 19F NMR. For complexes 2, 3, 4 conductivity data in acetone solutions are reported. The crystal structures of 2 and 3 were determined. NMR parameters of 1-5 and related complexes are discussed from the viewpoint of their isomerism. |
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| Keywords: | Rhodium(III) methyl complexes β-Diketonates Oxidative addition NMR X-ray |
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