Living Polymerization of Bulky Aryl Isocyanide with Arylrhodium Complexes
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Abstract
Well-defined arylrhodium complexes Rh(Ar)(nbd)(PPh3) (Ar = Me2C6H3, 2,4,6-Pri3C6H2, 2-PhC6H4, 2-Me-1-naphthyl, 9-anthracenyl, C(Ph)CPh2; nbd = 2,5-norbornadiene) that were prepared from the reaction of [Rh(nbd)Cl]2 with LiAr and PPh3 effectively initiated the living polymerization of aryl isocyanides possessing bulky substituents at the ortho position in the presence of PPh3 to give poly(isocyanide)s with narrow polydispersity indexes in good yields. The bulky aryl groups on the Rh complex were essential to achieving high initiator efficiency, whereas the bulky substituents on aryl isocyanides were required for the formation of high molecular weight polymers. The living nature of the present system was confirmed by kinetic studies as well as the formation of block copolymers. The polymerization rate was dependent not on the concentration of monomers, but on the concentration of PPh3.
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