Synthesis and reactivity of rhodium fluoro complexes

Catalytic CF Bond Activation of Hexafluoropropene by Rhodium: Formation of (3,3,3‐Trifluoropropyl)silanes

“…In principle 1 a can be regenerated from 3 by reaction of 3 with a tertiary silane 10. 17 We have no indication that cis‐fac‐ [Rh(H) 2 (SiPh 3 )(PEt 3 ) 3 ] ( 5 ) serves as dihydrogen source because we did not observe any loss of H 2 from 5 in stoichiometric experiments. Instead 5 was found to liberate only Ph 3 SiH.…”

Synthesis of Fluorinated Building Blocks by Transition‐Metal‐Mediated Hydrodefluorination Reactions

“…Repeated HDF steps eventually afford 3,3,3‐trifluoropropene; hydrogenation of the 3,3,3‐trifluoropropene to trifluoropropane is catalyzed by 49 . The fluorido complex 63 may for example originate from protonolysis of 49 , 62 , or another intermediate Rh vinyl species by triethylamine⋅HF33 and can be reconverted into 49 by treatment with triphenylsilane, thus completing a cyclic process. Replacing dihydrogen by other hydrogen–element reagents allows for CF bond functionalization beyond hydrodefluorination.…”

A Highly Reactive Rhodium(I)–Boryl Complex as a Useful Tool for CH Bond Activation and Catalytic CF Bond Borylation

“…Moreover, we found that 3 can be generated in a comparable reaction, starting from the fluoro compound [Rh(F)(PEt 3 ) 3 ] (4). [14] The fluoroborane FBpin that was also formed can be removed in vacuo. Note that boryl complex 3 does not react with another equivalent of B 2 pin 2 to give a Rh III complex that would be comparable to fac-[Rh(Bcat) 3 (PMe 3 ) 3 ].…”