Abstract
Reactions of [Rh(η5-C5H5)(CO)2] with isomeric primary and secondary fluoroalkyl iodides proceed by selective fluoroalkylation at the metal center to give [Rh(η5-C5H5)(CO)(RF)I], and treatment of these compounds with excess PMe3 affords cationic fluoroalkyl complexes [Rh(η5-C5H5)(PMe3)2(RF)]+I-. In contrast, reactions of [Rh(η5-C5H5)(PMe3)2] with the same fluoroalkyl iodides proceed with completely different selectivity to afford ring-exo-fluoroalkylated products [Rh(η4-C5H5RF)(PMe3)2I], which, in turn, react with Ag+BF4- to give the cationic hydrido complexes [Rh(η5-C5H4RF)(PMe3)2H]+[BF4]-.
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