A series of new fluororhodium(I) complexes †

Abstract

The reaction of [Rh{η²-O₂S(O)CF₃}(PPrⁱ₃)₂] 1 with terminal alkynes RC[triple bond, length half m-dash]CH (R = Ph or Bu^t) led to the formation of the vinylidene compounds trans-[Rh{η¹-OS(O)₂CF₃}([double bond, length half m-dash]C[double bond, length half m-dash]CHR)(PPrⁱ₃)₂] 2a,2b, which on treatment with tetrabutylammonium fluoride hydrate or KF gave the fluororhodium(I) complexes trans-[RhF([double bond, length half m-dash]C[double bond, length half m-dash]CHR)(PPrⁱ₃)₂] 3a,3b in ca. 70% yield. An alternative route for the preparation of 3a (R = Ph) is based on the reaction of phenylacetylene with the dimer [{Rh(µ-F)(PPrⁱ₃)₂}₂] 4, the latter being obtained from 1 and [NBu₄]F hydrate as starting materials. Compound 4 reacts smoothly with L′ = CO, CNC₆H₃Me₂-2,6, C₂Ph₂ and C₂H₄ to afford the mononuclear complexes trans-[RhF(L′)(PPrⁱ₃)₂], of which that with L′ = C₂H₄ was characterized by X-ray crystallography. In contrast to the hydroxo compound trans-[Rh(OH)([double bond, length half m-dash]C[double bond, length half m-dash]CHPh)(PPrⁱ₃)₂], which on treatment with acids HX (X = CF₃SO₃, CH₃CO₂, PhO or PhC[triple bond, length half m-dash]C) gave trans-[RhX([double bond, length half m-dash]C[double bond, length half m-dash]CHPh)(PPrⁱ₃)₂], the fluoro derivative 3a reacts only with CF₃SO₃H and PhC[triple bond, length half m-dash]CH by ligand substitution to yield the corresponding compounds. Acetic acid and phenol interact with 3a via XH  · · ·  FRh hydrogen bridges to form 1∶1 adducts, of which that with X = CH₃CO₂ rearranges to give trans-[Rh(O₂CMe)([double bond, length half m-dash]C[double bond, length half m-dash]CHPh)(PPrⁱ₃)₂] and probably trans-[Rh(FHF)([double bond, length half m-dash]C[double bond, length half m-dash]CHPh)(PPrⁱ₃)₂].

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