Metal to ligand group transfer reactions : II. Reactions of some π-allylrhodium(I) complexes with trifluoroacetic acid and alkyl,acyl and trimethyltin halides |
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| Authors: | John F Nixon John S. Poland Brian Wilkins |
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| Affiliation: | School of Molecular Sciences, University of Sussex, Brighton BN1 9QJ Great Britain |
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| Abstract: | Rh(π-C3H5)(PF3)3 (I), reacts with trifluoroacetic acid to form propene and [Rh(CF3COO)(PF3)2]2 (II). I reacts with t-butyl bromide to give [RhBr(PF3)2]2 and a mixture of propene and 2-methyl-1-propene and with n-propyl bromide to give propene and [RhBr(PF3)2]2. Rh(π-C3H5)(PPh3)2 (III), and t-butyl bromide yield propene and 2-methyl-1-propene. In these reactions a mechanism involving β-hydrogen abstraction and hydrogen migration via the metal to carbon is proposed. When III reacts with Me3SnCl the Me3Sn—moiety migrates intact to the π-allyl group. I reacts with acetyl chloride to give propene, [RhCl(PF3)2]2 and the carbonyl rhodium complex Rh2Cl2(PF3)3(CO). II does not apparently undergo phosphine ligand exchange unlike the analogous halogeno-bridged dimers. |
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