Synthesis and structure of rhodium(i) silyl carbonyl complexes: photochemical C-F and C-H bond activation of fluorinated aromatic compounds.

The rhodium(i) silyl carbonyl complexes [Rh{Si(OEt)3}(CO)(dippp)] () and [Rh{Si(OEt)3}(CO)(dippe)] () (dippp = 1,3-bis(diisopropylphosphino)propane, dippe = 1,2-bis-(diisopropylphosphino)ethane) were synthesized on treatment of the methyl compounds [Rh(CH3)(CO)(dippp)] () or [Rh(CH3)(CO)(dippe)] () with HSi(OEt)3 at low temperature. The methyl complexes and were prepared starting from the binuclear complexes [{Rh(μ-Cl)(dippp)}2] () and [{Rh(μ-Cl)(dippe)}2] (), respectively. The silyl complexes and as well as the precursors [{Rh(μ-I)(dippp)}2] (), [Rh(X)(CO)(dippp)] (: X = CH3, : X = I) and [Rh(X)(CO)(dippe)] (: X = CH3, : X = Cl) were characterized by NMR and IR spectroscopy and the structures in the solid state were determined by X-ray crystallography. The silyl complex converts into the carbonyl-bridged complex [{Rh(μ-CO)(dippp)}2] () above temperatures of -30 °C by loss of the silyl ligand, whereas is more thermally stable and a reaction to the binuclear complex [{Rh(μ-CO)(dippe)}2] () was observed at 50 °C. The silyl complex reacted under irradiation with hexafluorobenzene and pentafluoropyridine to give the C-F activation products [Rh(C6F5)(CO)(dippe)] () and [Rh(2-C5F4N)(CO)(dippe)] (), respectively. As additional products the silyl dicarbonyl complex [Rh{Si(OEt)3}(CO)2(dippe)] () and the cationic complex [Rh2(μ-H)(μ-CO)2(dippe)2](+)[SiF5](-) () were identified. Compound was synthesized independently by treatment of with gaseous CO. In a similar manner, the dippp analogue [Rh{Si(OEt)3}(CO)2(dippp)] () was also prepared starting from . Photochemical reaction of with pentafluorobenzene and 2,3,5,6-tetrafluoropyridine resulted selectively in C-H bond activation to afford and [Rh(4-C5F4N)(CO)(dippe)] (), respectively.