Fast Controlled Living Polymerization of Arylisocyanide Initiated by Aromatic Nucleophile Adduct of Nickel Isocyanide Complex

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• 作者：Sadayuki Asaoka ; Ayako Joza ; Sakiko Minagawa ; Lijun Song ; Yukimitsu Suzuki ; Tomokazu Iyoda
• 刊名：ACS Macro Letters
• 出版年：2013
• 出版时间：October 15, 2013
• 年：2013
• 卷：2
• 期：10
• 页码：906-911
• 全文大小：330K
• 年卷期：v.2,no.10(October 15, 2013)
• ISSN：2161-1653

文摘

The fast living polymerization of chiral arylisocyanide in the presence of the aromatic nucleophile adduct of tetra(t-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.