10.1021/mz400410y.s002 Sadayuki Asaoka Sadayuki Asaoka Ayako Joza Ayako Joza Sakiko Minagawa Sakiko Minagawa Lijun Song Lijun Song Yukimitsu Suzuki Yukimitsu Suzuki Tomokazu Iyoda Tomokazu Iyoda Fast Controlled Living Polymerization of Arylisocyanide Initiated by Aromatic Nucleophile Adduct of Nickel Isocyanide Complex American Chemical Society 2016 Fast Controlled Living Polymerization polymer products NMR studies chiral arylisocyanide Aromatic Nucleophile Adduct chain transfer polydispersity initiator Arylisocyanide Initiated nucleophile adduct MS Nickel Isocyanide ComplexThe monomer 2016-02-18 15:58:22 Dataset https://acs.figshare.com/articles/dataset/Fast_Controlled_Living_Polymerization_of_Arylisocyanide_Initiated_by_Aromatic_Nucleophile_Adduct_of_Nickel_Isocyanide_Complex/2366755 The fast living polymerization of chiral arylisocyanide in the presence of the aromatic nucleophile adduct of tetra­(<i>t</i>-butylisocyano)­nickel­(II) complex as an initiator gave the predominantly one-handed helical polyisocyanide with narrow polydispersity. X-ray crystal structures of initiators and MALDI-TOF MS and NMR studies of the polymer products elucidated the key role of the aromatic substituents in the initiator and monomer achieving narrow polydispersity. The aromatic groups in the initiator and monomer stabilized the electronic structure of the carbene-like ligand to suppress dissociation of the active nickel complex that leads to chain transfer and termination. The aromatic groups also controlled the reactivity of the active site for initiation and propagation.