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

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.