Arene complexes of transition metals in reactions with nucleophilic reagents: XXX. Reaction of π-halomesitylene [Tetramethyl(ethyl)cyclopentadienyl]rhodium(II) complexes with anions derived from CH acids

Autor:	G. S. Zhilovskii, V. D. Shteingarts, N. M. Romanova, L. I. Goryunov
Rok vydání:	2007
Předmět:	Chemistry Ligand Organic Chemistry chemistry.chemical_element Medicinal chemistry Rhodium Diethyl malonate Solvent chemistry.chemical_compound Nucleophile Cyclopentadienyl complex Halogen Organic chemistry Malononitrile
Zdroj:	Russian Journal of Organic Chemistry. 43:1765-1772
ISSN:	1608-3393 1070-4280
DOI:	10.1134/s1070428007120056
Popis:	Reactions of fluoro-and chloromesitylene π-complexes [(η6-1-Hlg-2,4,6-Me3C6H2)(η5-C5EtMe4)Rh]-(BF4)2 (Hlg = F, Cl) with diethyl malonate anion in THF or acetone-d6 at 20°C initially (within the first 5–30 min) involve nucleophile addition at unsubstituted carbon atom in the arene ligand with formation of π-cyclohexadienyl complexes {[η5-1-(EtOCO)2CH-1-H-3-Hlg-2,4,6-Me3C6H2](η5-C5EtMe4)Rh}(BF4). The subsequent replacement of the halogen atom yields {[η6-1-(EtOCO)2CH-2,4,6-Me3C6H2](η5-C5EtMe4)Rh}(BF4)2, where the arene ligand is readily withdrawn from π-coordination by the action of chloride ion or the solvent. Dimethyl mesitylmalonate was isolated in 76% yield. Likewise, the reactions with anions derived from malononitrile and ethyl cyanoacetate gave 25–38% of the corresponding derivatives 1-R-2,4,6-Me3C6H2 where R = (NC)2CH or EtOCO(NC)CH.
Databáze:	OpenAIRE
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