Exploring the Reactivity of Na[W2(μ-Cl)3Cl4(THF)2]∙(THF)3 towards the Polymerization of Selected Cycloolefins

Nikolaos Saragas; Georgios Floros; Grigorios Raptopoulos; Marinos Pitsikalis; Patrina Paraskevopoulou; Konstantinos Mertis

doi:10.3390/molecules201219810

Exploring the Reactivity of Na[W2(μ-Cl)3Cl4(THF)2]∙(THF)3 towards the Polymerization of Selected Cycloolefins

Molecules. 2015 Dec 8;20(12):21896-908. doi: 10.3390/molecules201219810.

Authors

Nikolaos Saragas¹, Georgios Floros², Grigorios Raptopoulos³, Marinos Pitsikalis⁴, Patrina Paraskevopoulou⁵, Konstantinos Mertis⁶

Affiliations

¹ Department of Inorganic Chemistry, Faculty of Chemistry, University of Athens, Panepistimiopolis Zografou, Athens 15771, Greece. nsaragas@sch.gr.
² Department of Inorganic Chemistry, Faculty of Chemistry, University of Athens, Panepistimiopolis Zografou, Athens 15771, Greece. geofloros@chem.uoa.gr.
³ Department of Inorganic Chemistry, Faculty of Chemistry, University of Athens, Panepistimiopolis Zografou, Athens 15771, Greece. grigorisrap@chem.uoa.gr.
⁴ Department of Industrial Chemistry, Faculty of Chemistry, University of Athens, Panepistimiopolis Zografou, Athens 15771, Greece. pitsikalis@chem.uoa.gr.
⁵ Department of Inorganic Chemistry, Faculty of Chemistry, University of Athens, Panepistimiopolis Zografou, Athens 15771, Greece. paraskevopoulou@chem.uoa.gr.
⁶ Department of Inorganic Chemistry, Faculty of Chemistry, University of Athens, Panepistimiopolis Zografou, Athens 15771, Greece. cmertis@chem.uoa.gr.

Abstract

The bimetallic compound Na[W2(μ-Cl)3Cl4(THF)2]·(THF)₃ (1, {W (3) W}(6+), a'2e'4) is a highly efficient room-temperature initiator for ring opening metathesis polymerization (ROMP) of norbornene (NBE) and some of its derivatives. In most cases, addition of phenylacetylene (PA) as co-initiator improves the catalytic activity and retains the high cis-stereoselectivity. On the other hand, 1 can polymerize cyclopentadiene (CPD), not via a metathetic, but rather, via a cationic mechanism. Here, we present a comparison of the reactivity of the two catalytic systems (1 and 1/PA) between themselves and with other systems reported in the literature, the characterization of the polymers formed and mechanistic aspects of the corresponding reactions.

Keywords: ROMP; metal-metal bonds; metathesis; tungsten.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Anhydrides / chemistry*
Catalysis
Coordination Complexes / chemistry*
Crystallography, X-Ray
Cycloparaffins / chemistry*
Models, Molecular
Molecular Structure
Norbornanes / chemistry*
Organometallic Compounds / chemistry*
Polymerization
Polymers / chemistry*

Substances

Anhydrides
Coordination Complexes
Cycloparaffins
Norbornanes
Organometallic Compounds
Polymers
norbornene anhydride