Reactions of Perfluoroalkyl Iodides with M(C5H5)(CO)(PMe3) [M = Rh, Ir]; Evidence for Direct Fluoroalkylation at a CO Ligand
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Abstract
While reaction of n-C3F7I with CpRh(PMe3)(CO) gives the expected product of oxidative addition, CpRh(PMe3)(nC3F7)(I), the analogous reaction of iso-C3F7I affords a mixture of CpRh(PMe3)(CF(CF3)2)(I) and the perfluoroacyl complex CpRh(PMe3)(COCF(CF3)2)(I). The latter compound is not formed from the former by a migratory insertion reaction. In further contrast, low-temperature reaction of CpIr(CO)(PMe3) with n-C3F7I gives the ionic complex [CpIr(CO)(PMe3)(nC3F7)]+I-, which is inert to thermal substitution; treatment with N-methylmorpholine-N-oxide (NMO) results in CO oxidation and iodide coordination to give CpIr(PMe3)(nC3F7)(I). The same reaction at room temperature affords a mixture of four products, including small amounts of [CpIr(CO)(PMe3)(nC3F7)]+I- and CpIr(PMe3)(nC3F7)(I); the major components are the perfluoroacyl complex CpIr(PMe3)(COnC3F7)(I) and the perfluoroacyl(perfluoroalkyl) complex CpIr(PMe3)(COnC3F7)(nC3F7). Crystallographic structure determinations of all these molecules are reported, and a mechanism involving direct fluoroalkylation at CO is proposed.
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