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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