The Open Macromolecules Journal

2008, 2 : 32-37
Published online 2008 October 23. DOI: 10.2174/1874343900802010032
Publisher ID: TOMACROJ-2-32

Halogenated Olefins as Chain Transfer Agents in the Synthesis of Telechelic Polynorbornenes Using Ruthenium Alkylidene Catalysts. Computational and Experimental Studies

Joel Vargas , Serguei Fomine , Lioudmila Fomina and Mikhail A. Tlenkopatchev
Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, México DF 04510, México.

ABSTRACT

Ring-opening metathesis polymerization (ROMP) of norbornene (NB) and its derivatives N-adamantyl-exoendo- norbornene-5,6-dicarboximide (AdNDI) and N-cyclohexyl-exo-endo-norbornene-5,6-dicarboximide (CyNDI) in the presence of cis-1,4-dichloro-2-butene (2a) and cis-1,2-dichloro-ethylene (2b) as chain transfer agents (CTAs) using a [1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolilydene] (PCy3)Cl2Ru=CHPh (I) has been studied. α Halogenated olefin 2b shows no activity as a CTA when β halogenated olefin 2a is readily cross-metathesized with NB and norbornene dicarboximides. The chain transfer reaction pathways during the ROMP of NB to 2b using a (1,3-diphenyl-4,5- dihydroimidazol-2-ylidene) (PCy3)Cl2Ru=CHPh (1) have been studied at B3LYP/LACVP* level of theory. The calculations show that 2b is a poor substrate for the metathesis reaction due to the steric effect produced by chlorine atoms directly linked to the double bond. The calculated Gibbs free activation energy of a chain transfer reaction from ring-opened NB to 2b was 25.1 kcal/mol.

Keywords:

Halogenated olefins, telechelic polynorbornene, ruthenium alkylidene.