Issue 20, 2008
From the journal:

Dalton Transactions

Synthesis of palladium(ii) complexes containing a new α-d-xylofuranose-modified diphosphine and their application as catalyst precursors in the co- and terpolymerization of CO–ethene and propene†

Bianca K. Muñoz-Moreno,a   Carmen Claver,*a   Aurora Ruiz,a   Claudio Bianchini,*b   Andrea Melib  and  Werner Oberhauser*b  

* Corresponding authors

a Dept. de Química Física i Inorganica, Facultat de Química, Universitat Rovira i Virgili, c/Marcel.li Domingo s/n, Tarragona, Spain
E-mail: carmen.claver@urv.cat
Fax: +34-977-559563

b Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), Area di Ricerca CNR di Firenze, via Madonna del Piano 10, Sesto Fiorentino, Italy
E-mail: claudio.bianchini@iccom.cnr.it; werner.oberhauser@iccom.cnr.it
Fax: +39-055-5225203

Abstract

The diphosphine 3,5-dideoxy-1,2-O-isopropylidene-3,5-bis(di(2-methoxyphenyl)phosphanyl)-α-D-xylofuranose (o-MeO-xylophos), which differs from the known 3,5-dideoxy-1,2-O-isopropylidene-3,5-bis(diphenylphosphanyl)-α-D-xylofuranose (xylophos) by the presence of 2-methoxy substituents on the P-aryl rings, has been synthesized and characterized. These two ligands have been employed to stabilize the PdII complexes [PdCl2(o-MeO-xylophos)] (1a), [PdCl2(xylophos)] (2a), [PdClMe(o-MeO-xylophos)] (1b), [PdClMe(xylophos)] (2b), [Pd(OTs)(H2O)(o-MeO-xylophos)](OTs) (1c) and [Pd(OTs)(H2O)(xylophos)](OTs) (2c). All complexes have been characterized by multinuclear-NMR spectroscopy. The solid-state structure of 1a has been determined by a single crystal X-ray analysis. The Pd–aqua complexes 1c and 2c have been employed to catalyse the CO–ethene and CO–propene copolymerization as well as the CO–ethene–propene terpolymerization reaction in MeOH. The catalytic activity and the molecular weight of the polyketones have been compared to those of the products obtained with analogous catalysts, [Pd(H2O)2(o-MeO-dppp)](OTs)2 (3c) and [Pd(H2O)(OTs)(dppp)](OTs) (4c), bearing the classical 1,3-bis(diphenylphoshino)propane ligand (dppp). Under comparable catalytic conditions, all catalysts produce structurally similar polymeric materials, with 1c yielding the largest propene incorporation as well as the highest productivity of low-molecular-weight terpolymers.

Graphical abstract: Synthesis of palladium(ii) complexes containing a new α-d-xylofuranose-modified diphosphine and their application as catalyst precursors in the co- and terpolymerization of CO–ethene and propene

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Article information

DOI
https://doi.org/10.1039/B719748A
Article type
Paper
Submitted
21 Dec 2007
Accepted
18 Feb 2008
First published
31 Mar 2008

Dalton Trans., 2008, 2741-2750

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Synthesis of palladium(II) complexes containing a new α-D-xylofuranose-modified diphosphine and their application as catalyst precursors in the co- and terpolymerization of CO–ethene and propene

B. K. Muñoz-Moreno, C. Claver, A. Ruiz, C. Bianchini, A. Meli and W. Oberhauser, Dalton Trans., 2008, 2741 DOI: 10.1039/B719748A

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