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New complexes of palladium(II) with chelating heterocyclic nitrogen ligands: characterization and catalytic activity in CO-styrene copolymerization: crystal structure of [Pd(bipy)2][BAr'4]2; Ar'[3,5-(CF3)2C6H3]

Stoccoro, Sergio and Alesso, Giuseppe Andrea and Cinellu, Maria Agostina and Minghetti, Giovanni and Zucca, Antonio and Bastero Rezola, Amaya and Claver, Carmen and Manassero, Mario (2002) New complexes of palladium(II) with chelating heterocyclic nitrogen ligands: characterization and catalytic activity in CO-styrene copolymerization: crystal structure of [Pd(bipy)2][BAr'4]2; Ar'[3,5-(CF3)2C6H3]. Journal of Organometallic Chemistry, Vol. 664 (1-2), p. 77-84. ISSN 0022-328X. Article.

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DOI: 10.1016/S0022-328X(02)01966-6

Abstract

New bis-chelated palladium(II) derivatives [Pd(bipyR)2]2+ and [Pd(bipy)(bipyR)]2+ (bipy=2,2'-bypiridine, bipyR= 6-Me, 6-Et, 6-i -Pr-2,2'-bipyridine) have been isolated as [BAr'4]- salts (Ar'=[3,5-(CF3)2C6H3]) and tested as catalyst precursors in the CO- styrene or 4-tert -butylstyrene (TBS) copolymerization. The comparison of their activity with that of [Pd(bipy)2][BAr'4]2 prepared for comparative purpose shows that the presence of a 6-substituent on the bipy has a negative effect. On the other hand, comparison of the activities of [Pd(bipy)2][BAr'4]2 and [Pd(bipy)2][PF6]2, reported to be one of the best catalytic precursors for this reaction, shows that the [BAr'4] anion increases the activity under various reaction conditions. The results obtained with [Pd(bipy)2][BAr'4 ]2 at low pressure (pCO/10 atm) are among the best reported for this type of precatalysts. A study related to the use of 2,2,2-trifluoroethanol (TFE), as solvent, allows the optimisation of the amount of alcohol required for the copolymerization reaction. The X-ray structure of [Pd(bipy)2][BAr'4]2 shows that the conformation of the cation is similar to that observed in the corresponding [BF4] salt, but remarkably different from that of [Pd(bipy)2][PF6]2.

Item Type:Article
ID Code:5347
Status:Published
Refereed:Yes
Uncontrolled Keywords:Catalysis, copolymerization, styrene, palladium complexes, nitrogen ligands, X-ray
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Publisher:Elsevier
ISSN:0022-328X
Publisher Policy:© 2002 Elsevier Science
Deposited On:27 Jan 2011 10:24

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