Linked Life Data

16807965

Source:http://linkedlifedata.com/resource/pubmed/id/16807965

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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
29
pubmed:dateCreated
2006-11-6
pubmed:abstractText
A series of cationic palladium complexes of general formula [Pd(Me)(MeCN)(N-N)][PF(6)] (N-N = (phen) 1 a, 4,7-dichloro-1,10-phenanthroline (4,7-Cl(2)-phen) 2 a, 4,7-diphenyl-1,10-phenanthroline (4,7-Ph(2)-phen) 3 a, 4-methyl-1,10-phenanthroline (4-Me-phen) 4 a, 4,7-dimethyl-1,10-phenanthroline (4,7-Me(2)-phen) 5 a, 5,5,6,6-tetrafluoro-5,6-dihydro-1,10-phenanthroline (F(4)-phen) 6 a, containing different substituted phenanthroline ligands, have been prepared from the corresponding neutral chloro derivatives [Pd(Me)(Cl)(N-N)], (1 b-6 b). The X-ray crystal structure of [Pd(Cl)(2)(4,7-Cl(2)-phen)] (2 b') was determined. DFT calculations show that the electron density on the metal is tuned by the substituents on the ligands. The catalytic behavior of complexes 1 a-6 a in the CO/styrene and CO/p-Me-styrene copolymerizations was studied in detail, showing that the generated catalysts are active for at least 90 h, yielding copolymers of high molecular weight. A firm correlation between the electron density on palladium on the one hand and the catalytic activity of the complexes and the molecular weight and the stereochemistry of the polyketones synthesized on the other hand has been established: the catalyst containing the F(4)-phen is thus far the most active among those tested, yielding the syndiotactic CO/styrene copolymer with a stereoregularity of 96 % (uu triad) and with an M(w) value of 1 000 000.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Oct
pubmed:issn
0947-6539
pubmed:author
pubmed:issnType
Print
pubmed:day
10
pubmed:volume
12
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
7639-51
pubmed:dateRevised
2009-8-4
pubmed:year
2006
pubmed:articleTitle
Long-lived palladium catalysts for CO/vinyl arene polyketones synthesis: a solution to deactivation problems.
pubmed:affiliation
Dipartimento di Scienze Chimiche, Università di Trieste Via Licio Giorgieri 1, 34127 Trieste, Italy.
pubmed:publicationType
Journal Article