Efficient Pincer‐Ruthenium Catalysts for Kharasch Addition of Carbon Tetrachloride to Styrene

Abstract A series of NNN pincer‐ruthenium complexes ( R2 NNN)RuCl 2 (PPh 3 ) (R=Cyclohexyl (Cy), t ‐butyl ( t Bu), i ‐propyl ( i Pr) and phenyl (Ph)) have been synthesized and characterized. These pincer‐ruthenium complexes have been used to catalyse the Kharasch addition or atom transfer radical addition (ATRA) of carbon tetrachloride to styrene. Among the pincer‐ruthenium catalysts screened for the Kharasch addition, the catalytic activity followed the order ( Cy2 NNN)RuCl 2 (PPh 3 )>( i Pr2 NNN)RuCl 2 (PPh 3 )≫( Ph2 NNN)RuCl 2 (PPh 3 ). The oxidation of Ru(II) is easier with ( Cy2 NNN)RuCl 2 (PPh 3 ) and ( i Pr2 NNN)RuCl 2 (PPh 3 ) in comparison with RuCl 2 (PPh 3 ) as indicated by cyclic voltammetry studies. The catalyst precursor ( R2 NNN)RuCl 2 (PPh 3 ) itself is the resting state of the reaction. The rate determining step involves the generation of the five‐coordinate 16‐electron ruthenium(II) species ( R2 NNN)RuCl 2 . Owing to weaker binding of triphenyl phosphine to ruthenium, the generation of catalytically active 16‐electron species ( Cy2 NNN)RuCl 2 and ( i Pr2 NNN)RuCl 2 are more favourable. The complex ( Cy2 NNN)RuCl 2 (PPh 3 ) demonstrates very high productivity (5670 turnovers after 48 h at 140 °C) in the absence of any co‐catalyst radical initiator. To the best of our knowledge, our turnovers (ca. 5670) are much higher than that reported hitherto. Quantum mechanical calculations demonstrate that the path involving the activation of carbon tetrachloride by ( Cy2 NNN)RuCl 2 is more favoured than the path where carbon tetrachloride is activated by ( Cy2 NNN)RuCl 2 ( η 2 ‐styrene) . Density functional theory (DFT) and kinetic studies are in accord with the widely accepted mechanism involving the single electron transfer (SET) from ruthenium(II) to chloride radical with concomitant generation of a benzyl radical which is trapped by the resulting ruthenium(III) species. magnified image