Activation and Derivatization of Perfluoro(methyl Vinyl Ether) by a Rh(I) Germyl Complex

The reactivity of [Rh(GePh 3 )(PEt 3 ) 3 ] ( 1 ) with perfluoro(methyl vinyl ether) [PMVE, CF 2 CF(OCF 3 )] is investigated. The reaction proceeds via CO bond activation of PMVE and transformation of the OCF 3 into carbonyl ligands. Concomitant release of FGePh 3 ultimately furnishes the fluorovinyl rhodium complex trans ‐[Rh(CFCF 2 )(CO)(PEt 3 ) 2 ] ( 2 ). Complex 2 is alternatively obtained by the reaction of the rhodium hydrido complex [Rh(H)(PEt 3 ) 3 ] ( 5 ) with chlorotrifluoroethylene in the presence of CO gas. In the absence of CO, the π‐bonded olefin complexes [Rh(Cl)(η 2 ‐CF 2 CFH)(PEt 3 ) 2 ] ( 7 ) and [Rh(Cl)(η 2 ‐CF 2 CFCl)(PEt 3 ) 2 ] ( 8 ) are formed. Although catalyst deactivation occurs rapidly due to carbonyl complex formation, catalytic derivatization of PMVE with HGePh 3 affords unique germane products such as CF 2 HCFHGePh 3 and CF(GePh 3 )CF 2 .