Competing reaction pathways of 3,3,3-trifluoropropene at rhodium hydrido, silyl and germyl complexes: C-F bond activation versus hydrogermylation.

The reaction of the silyl complex [Rh{Si(OEt)}(PEt)] (1) with 3,3,3-trifluoropropene afforded the rhodium complex [Rh(CHCHCF){Si(OEt)}(PEt)] (2) which features a bonded fluorinated olefin. In contrast the rhodium hydrido complex [Rh(H)(PEt)] (3) yielded on treatment with 3,3,3-trifluoropropene in the presence of a base the fluorido complex [Rh(F)(PEt)] (4) together with 1,1-difluoro-1-propene by C-F bond activation. At low temperature the intermediate fac-[Rh(H)(CHCHCF)(PEt)] (5) was detected by NMR spectroscopy.

Remarkable reactivity of a rhodium(I) boryl complex towards CO2 and CS2: isolation of a carbido complex.

The activation of CO2, CS2 as well as of PhNCO at [Rh(Bpin)(PEt3)3] led to C=X bond cleavage and the formation of {RhXBpin} species (X = O, S, N). Treatment of the boryl complex [Rh(Bpin)(PEt3)3] with 0.5 equivalents of CS2 resulted in the fragmentation of CS2 and the formation of the remarkable μ-carbido complex trans-[Rh2(μ-C)(SBpin)2(PEt3)4].

Catalytic C-H bond activation at nanoscale Lewis acidic aluminium fluorides: H/D exchange reactions at aromatic and aliphatic hydrocarbons.

Nanoscopic amorphous Lewis acidic aluminium fluorides, such as aluminium chlorofluoride (ACF) and high-surface aluminium fluoride (HS-AlF(3)), are capable of activating C-H bonds of aliphatic hydrocarbons. H/D exchange reactions are catalysed under mild conditions (40 °C).

C-F activation at rhodium boryl complexes: formation of 2-fluoroalkyl-1,3,2-dioxaborolanes by catalytic functionalization of hexafluoropropene.

Fluorinated building blocks by C-F bond cleavage: Catalytic C-F activation reactions that give novel dioxaborolanes have been developed (see scheme). The reactions proceed at room temperature, and catalytic intermediates are presumably rhodium hydride and boryl species.