Document Detail

Air-Stable (Phenylbuta-1,3-diynyl)palladium(II) Complexes: Highly Active Initiators for Living Polymerization of Isocyanides.
MedLine Citation:
PMID:  24605888     Owner:  NLM     Status:  Publisher    
A family of air-stable (phenylbuta-1,3-diynyl)palladium(II) complexes were designed and prepared in a facile synthetic procedure. Their structures were characterized by 1H and 13C NMR, MS and X-ray analysis. These Pd complexes were revealed to efficiently initiate the polymerization of phenyl isocyanides in a living/controlled chain growth manner, which led to the formation of poly(phenyl isocyanide)s with controlled molecular weights and narrow molecular weight distributions. 13C NMR analysis indicated the isolated poly(phenyl isocyanide) was of high stereoregularity. The Pd unit at the end of the polymer chain could undergo further copolymerization with phenyl isocyanide monomers to give block copolymers. It was also found that incorporation of an electron-donating group on the phenyl group of the Pd complex could improve the catalytic activities. Furthermore, these Pd complexes were tolerant to most organic solvents and applicable to a wide range of isocynide monomers including alkyl and phenyl isocyanides and even phenyl isocyanide with bulky substituent on the ortho position, and diisocyanide monomers. Therefore, this new polymerization system is versatile in the preparation of well-defined polyisocyanides with controlled structure and sequence. Bi- and tri-functional Pd complexes with two and three Pd units incorporated onto the same phenyl ring were designed and synthesized. They were also able to initiate the living polymerization of phenyl isocyanide to afford telechelic linear and star shaped polyisocyanides with controlled molecular weights and narrow molecular weights distributions.
Ya-Xin Xue; Yuan-Yuan Zhu; Long-Mei Gao; Xiao-Yue He; Na Liu; Wu-Yi Zhang; Jun Yin; Yunsheng Ding; Hongping Zhou; Zong-Quan Wu
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2014-3-7
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  -     ISSN:  1520-5126     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2014 Mar 
Date Detail:
Created Date:  2014-3-10     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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