Synthesis and reactivity of rhodium fluoro complexes

[RhH(CO)(PPh3)2] (1) reacts with Et3N·3HF to give the fluoro compound [RhF(CO)(PPh3)2] (2). In a comparable reaction [RhF(PEt3)3] (5) has been obtained from [RhH(PEt3)3] (3) or [RhH(PEt3)4] (4) with substoichiometric amounts of Et3N·3HF in THF. If the latter reaction is carried out in benzene, the complexes 5, cis-mer-[Rh(H)2F(PEt3)3] (6) and cis-fac-[Rh(H)2F(PEt3)3] (7) are obtained. Treatment of 5 with HCl in ether effects the generation of [RhCl(PEt3)3] (8) and the bifluoride compound [Rh(FHF)(PEt3)3] (9), which can be converted into 5 in the presence of Et3N and Cs2CO3. Treatment of 5 with HSiR2Ph (R=Ph, Me) leads to the formation of 3 and the rhodium(III) silyl complexes fac-[Rh(H)2(SiR2Ph)(PEt3)3] (10: R=Ph, 11: R=Me).