First Examples of Homogeneous Catalytic Cyclotrimerization and Polymerization of Phenylacetylene and Copolymerization of Phenylacetylene and Norbonene with Dinuclear Complexes Containing Unbridged Metal-Metal Quadruple Bond

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Title:First Examples of Homogeneous Catalytic Cyclotrimerization and Polymerization of Phenylacetylene and Copolymerization of Phenylacetylene and Norbonene with Dinuclear Complexes Containing Unbridged Metal-Metal Quadruple Bond
Creators:
Mertis, Konstantinos
Arbilias, Stavros
Argyris, Demos
Psaroudakis, Nikos
Vohlídal, Jiří
Lavastre, Olivier
Dixneuf, Pierre H.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 68, 6, pp. 1094-1104
Uncontrolled Keywords:Alkenes, ROMP, Molybdenum, Single-component catalysts, Alkynes, Dinuclear complexes, Rhenium, Tungsten, Metal-metal quadruple bond, Cyclotrimerizations, Metathesis polymerizations

Abstract

First examples of application of dinuclear complexes containing unbrigded metal-metal quadruple bond as catalysts in cyclotrimerization, oligomerization and polymerization of substituted acetylene are reported. The d<sup>4</sup>-d<sup>4</sup> dinuclear complexes (Bu<sub>4</sub>N)<sub>2</sub>[Re<sub>2</sub>X<sub>8</sub>] (<strong>1</strong>) (<strong>1a</strong>, X = Cl; <strong>1b</strong>, X = Br and <strong>1c</strong>, X = I) show low activity and the complex [Mo<sub>2</sub>Cl<sub>4</sub>(MeOH)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>] (<strong>2</strong>) medium activity in cyclotrimerization and oligomerization of phenylacetylene (PA). In contrast, the tungsten-based d<sup>4</sup>-d<sup>4</sup>, complex Na<sub>4</sub>[W<sub>2</sub>Cl<sub>8</sub>] (<strong>3</strong>) exhibits high polymerization activity (polymer yield above 90%) and <i>ca</i> 75% <i>cis</i>-selectivity in tetrahydrofuran. The activity and <i>cis</i>-stereoselectivity of these single-component catalysts decrease in the order <strong>3</strong> &gt;&gt; <strong>2</strong> &gt;&gt; <strong>1</strong>, which is proportional to the metal-metal quadruple bond propensity towards ligand addition reactions. Complex <strong>3</strong> induces metathesis polymerization of norbornene (NBE) to poly(cyclopentene-1,3-diylvinylene) with 82% <i>cis</i>-selectivity and copolymerization of PA and NBE to almost all-<i>cis</i> high-molecular-weight copolymer containing cyclopentene-1,3-diylvinylene units, which is free of longer sequences of both PA and NBE units. This suggests that also homopolymerization of PA with <strong>3</strong> proceeds by the metathesis mechanism and that the PA/NBE copolymer structure is close to the alternating one. <p>

Title:First Examples of Homogeneous Catalytic Cyclotrimerization and Polymerization of Phenylacetylene and Copolymerization of Phenylacetylene and Norbonene with Dinuclear Complexes Containing Unbridged Metal-Metal Quadruple Bond
Creators:
Mertis, Konstantinos
Arbilias, Stavros
Argyris, Demos
Psaroudakis, Nikos
Vohlídal, Jiří
Lavastre, Olivier
Dixneuf, Pierre H.
Uncontrolled Keywords:Alkenes, ROMP, Molybdenum, Single-component catalysts, Alkynes, Dinuclear complexes, Rhenium, Tungsten, Metal-metal quadruple bond, Cyclotrimerizations, Metathesis polymerizations
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:68
Number:6
Page Range:pp. 1094-1104
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20031094UNSPECIFIED
ID Code:2106
Item Type:Article
Deposited On:06 Feb 2009 17:15
Last Modified:06 Feb 2009 16:15

Citation

Mertis, Konstantinos; Arbilias, Stavros; Argyris, Demos; Psaroudakis, Nikos; Vohlídal, Jiří; Lavastre, Olivier; Dixneuf, Pierre H. (2003) First Examples of Homogeneous Catalytic Cyclotrimerization and Polymerization of Phenylacetylene and Copolymerization of Phenylacetylene and Norbonene with Dinuclear Complexes Containing Unbridged Metal-Metal Quadruple Bond. Collection of Czechoslovak Chemical Communications, 68 (6). pp. 1094-1104. ISSN 0010-0765

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