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)(4)] (4) with substoichiometric amounts of Et3N.3HF in THF. If the latter reaction is carried out in benzene, the complexes 5, cis-mer-[RhCl(PEt3)(3)] (6) and cis-fac-[Rh(H)(2)F(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 = Rh, 11: R = Me). (C) 2004 Elsevier B.V. All rights reserved.