Synthesis of a novel oxotungsten(VI) complex having a chelating bis(aryloxo) ligand and its catalytic behavior for ring-opening metathesis polymerization

An oxotungsten complex coordinated with O-S-O chelating bis(aryloxo) ligand, WO{S(4-Me-6-(BuC6H2O)-Bu-t)(2)}Cl-2 (1), was synthesized by the reaction of WOCl4 with 2,2'-S(4-Me-6-(BuC6H2OH)-Bu-t)(2). The structure of the complex 1 was determined by single-crystal X-ray analysis to have pseudo C,...

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Bibliographic Details
Published inChemistry letters no. 6; pp. 488 - 489
Main Authors Takashima, Y, Nakayama, Y, Harada, A
Format Journal Article
LanguageEnglish
Published TOKYO Chemical Soc Japan 01.06.2001
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
ALKYLIDENE COMPLEXES
OLEFIN METATHESIS
BEARING
NORBORNENE
ROMP
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Summary:An oxotungsten complex coordinated with O-S-O chelating bis(aryloxo) ligand, WO{S(4-Me-6-(BuC6H2O)-Bu-t)(2)}Cl-2 (1), was synthesized by the reaction of WOCl4 with 2,2'-S(4-Me-6-(BuC6H2OH)-Bu-t)(2). The structure of the complex 1 was determined by single-crystal X-ray analysis to have pseudo C,symmetry. The catalytic behavior of 1/AlEt3 system for the ring-opening metathesis polymerization of norbornene was studied. In this catalytic system, strong dependencies of cis/trans selectivity on the catalyst concentration and on the polymerization temperature were observed. With increasing catalyst concentration and with lowering polymerization temperature, the resulting poly(norbornene)s tend to have higher cis-regularity. Oppositely, trans-rich poly(norbornene)s were produced by the polymerization under low catalyst concentration and at high polymerization temperature. We propose that these observations might come from oxotungsten-aluminum interaction.
ISSN:0366-7022
1348-0715
DOI:10.1246/cl.2001.488