The role of 2‐iminopyrrolyl copper(I) complexes in the Reversible‐Deactivation Radical Polymerization of methyl methacrylate

The role of 2‐iminopyrrolyl copper(I) complexes in the Reversible‐Deactivation Radical Polymerization (RDRP) of methyl methacrylate (MMA) is described. Mononuclear 2‐iminopyrrolyl copper(I) complexes [Cu{κ 2 N , N′ ‐NC 4 H 3 ‐2‐C(H)=NR′}L n ] 1 – 7 (R′ = C 6 H 5 , L n = (PPh 3 ) 2 ( 1 ); R′ = 2,6‐Me 2 C 6 H 3 , L n = (PPh 3 ) 2 ( 2 ); R′ = 2,6‐ i Pr 2 C 6 H 3 , L n = (PPh 3 ) 2 ( 3 ); R′ = 4‐NMe 2 C 6 H 4 , L n = (PPh 3 ) 2 ( 4 ); R′ = CH 3 , L n = (PPh 3 ) 2 ( 5 ); R′ = CH 3 , L n = (PMe 3 ) 2 ( 6 ); R′ = CH 3 , L n = P i Pr 3 ( 7 )) were synthesized by the reaction of the in situ prepared sodium salts of precursors HL1–5 with [Cu(NCMe) 4 ]BF 4 with the respective phosphines. In their absence, the binuclear complex [Cu{κ N ,κ N' ‐NC 4 H 3 ‐2‐C(H)=NCH 3 }] 2 8 was formed instead, which, when treated with one equivalent of PR 3 yielded the binuclear complexes [Cu 2 {κ N ,κ N' ‐NC 4 H 3 ‐2‐C(H)=NCH 3 } 2 PR 3 ] 9 (R = Ph) and 10 (R = Me). All complexes, except 8 , were active in the RDRP of MMA using the initiator tert ‐butyl‐α‐bromoisobutyrate ( t BiB‐Br), achieving apparent propagation kinetic constants (k p ') in the range of 0.5–7.5 × 10 −5 s −1 , at 90 °C and with a [MMA] 0 :[complex] 0 :[ t BiB‐Br] 0 ratio of 500:1:1. All reactions yielded poly (methyl methacrylate)s with molecular weights ( ) and dispersities higher than expected for Controlled Radical Polymerization processes. Complex 7 achieved the best results, with values being only 1.2‐fold higher than theoretically expected. Experimental and density functional theory (DFT) studies suggest that this system operates via Atom Transfer Radical Polymerization/Organometallic Mediated Radical Polymerization (ATRP/OMRP) mechanisms interplay.