Huang, Dejian published the artcileFacile and Reversible Cleavage of C-F Bonds. Contrasting Thermodynamic Selectivity for Ru-CF2H vs F-Os:CFH, Application of Trimethyl(perfluorophenyl)silane, the publication is Journal of the American Chemical Society (2000), 122(37), 8916-8931, database is CAplus.
In the presence of a catalytic amount of F– (CsF), Me3SiRf (Rf = CF3 and C6F5) exchanges Rf with fluoride of the 16-electron complexes MHF(CO)L2 (M = Ru, Os; L = PiPr3, PtBu2Me) to give Me3Si-F and the unsaturated pentafluorophenyl complexes, MH(C6F5)(CO)L2, or (when Rf = CF3) saturated fluorocarbene complexes, MHF(CF2)(CO)L2, via ¦Á-F migration. X-ray crystal structure and solution 19F NMR studies reveal that, in the ground state, the three atoms of the CF2 group lie in a plane perpendicular to the P-Ru-P axis so that the ¦Ð-back-donation is maximized and the carbene substituents are inequivalent. Having hydride trans to the CF2 ligand, MHF(CF2)(CO)L2 is a kinetic product, which converts to a thermodn. isomer. For Ru, the final product is a 16e complex, RuF(CF2H)(CO)L2, formed by combination of CF2 and hydride. For Os, the product is an 18e complex, OsF2(:CFH)(CO)L2, resulting from exchange of one carbene fluoride with the hydride. The distinct difference between Os and Ru demonstrates the principle that 3rd-row transition metals show a pronounced tendency toward a higher oxidation state. The isomerization mechanism involves phosphine dissociation as a slow step. Coordinatively saturated RuHF(CF2)(CO)L2 reacts with CO within the time of mixing to give the F and CF2 recombination product, RuH(CF3)(CO)2L2. This unexpectedly fast carbonylation reaction, as well as 19F spin saturation transfer experiments, reveals the existence of a fast ¦Á-F migration equilibrium between RuHF(CF2)(CO)L2 and RuH(CF3)(CO)L2 in solution In sharp contrast, the Os analog does not have such a fast equilibrium, and therefore it does not react with CO at room temperature At higher temperature, reaction occurs forming the hydride and fluoride exchanged product, Os(CHF2)(F)(CO)2L2. The contrasting behavior of Ru vs. Os regarding stability of fluoroalkyl and fluorocarbene is discussed on the basis of the theor. calculations, which also provide insight into the isomerization of RuHF(CF2)(CO)L2. Hydrogenolysis of Ru(CF2H)F(CO)L2 liberates CH2F2, forming RuHF(CO)L2.
Journal of the American Chemical Society published new progress about 1206-46-8. 1206-46-8 belongs to catalysis-chemistry, auxiliary class Organic Silicones, name is Trimethyl(perfluorophenyl)silane, and the molecular formula is C9H9F5Si, Application of Trimethyl(perfluorophenyl)silane.
Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia