Mechanistic insights into polar monomer insertion polymerization from acrylamides.

N-Isopropyl acrylamide (NIPAM), N,N-dimethyl acrylamide (DMAA), and 2-acetamidoethyl acrylate (AcAMEA) were copolymerized with ethylene employing [(P^O)PdMe(DMSO)] (1-DMSO; P^O = κ(2)-P,O-Ar(2)PC(6)H(4)SO(2)O with Ar = 2-MeOC(6)H(4)) as a catalyst precursor. Inhibition studies with nonpolymerizable polar additives show that reversible κ-O-coordination of free amide retards polymerization significantly. Retardation of polymerization increases in the order ethyl acetate ≪ methyl ethyl sulfone < acetonitrile < N,N-dimethylacetamide ≈ N-methylacetamide ≈ propionic acid < dimethylsulfoxide. Pseudo-first-order rate constants for the insertion into 1-DMSO were determined to increase in the order DMAA < AcAMEA < NIPAM < methyl acrylate. Exposure of 1-DMSO to NIPAM resulted in the formation of consecutive insertion products [(P^O)Pd(C(6)H(11)NO(2))(n)Me] (n ≤ 3), as determined by electrospray ionization mass spectrometry. The solid-state structure of the methanol adduct of the 2,1-insertion product of NIPAM into 1-DMSO, [(P^O)Pd{η(1)-CH(CONHiPr)CH(2)CH(3)}(κ(1)-O-MeOD)] (2-MeOD), was determined by single crystal X-ray diffraction. Both 2,1- and 1,2-insertions of DMAA into the Pd-Me bond of a [(P^O)PdMe] fragment occur to afford a ca. 4:1 mixture of chelates [(P^O)Pd{κ(2)-C,O-C(CH(2)CH(3))C(O)NMe(2)}] (3) and [(P^O)Pd{κ(2)-C,O-CH(2)C(CH(3))C(O)NMe(2)}] (4). The four-membered chelate of 3 is opened by coordination of 2,6-lutidine (3 + 2,6-lutidine ⇌ 3-LUT) with ΔH° = -41.8(10.5) kJ and ΔS° = -115(37) J mol(-1) K(-1).