Synthesis, Interionic Structure, and Reactivity toward CO and p-Methylstyrene of Palladacyclic Compounds Bearing α-Diimine Ligands

Palladacyclic compounds [Pd(C6H4(C6H5CO)CNR)(NN)] [X] (R = Et, iPr, 2,6‐iPr2C6H3; NN = bpy = 2,2′‐bipyridine, or 1,4‐(o,o′‐dialkylaryl)‐1,4‐diazabuta‐1,3‐dienes; [X]− = [BF4]− or [PF6]−) were synthesized from the dimers [{Pd(C6H4(C6H5CO)CNR)(μ‐Cl)}2] and NN ligands. Their interionic structu...

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Bibliographic Details
Published in:Helvetica chimica acta 2006-08, Vol.89 (8), p.1524-1546
Main Authors: Zuccaccia, Cristiano, Bellachioma, Gianfranco, Cardaci, Giuseppe, Macchioni, Alceo, Binotti, Barbara, Carfagna, Carla
Format: Article
Language:English
Subjects:
CO Insertion
Copolymerization
NMR Spectroscopy
Olefin insertion
p-methyl
Palladacycles
Polymerization
Styrene
Styrene, p‐methyl
X-Ray crystallography
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Summary:Palladacyclic compounds [Pd(C6H4(C6H5CO)CNR)(NN)] [X] (R = Et, iPr, 2,6‐iPr2C6H3; NN = bpy = 2,2′‐bipyridine, or 1,4‐(o,o′‐dialkylaryl)‐1,4‐diazabuta‐1,3‐dienes; [X]− = [BF4]− or [PF6]−) were synthesized from the dimers [{Pd(C6H4(C6H5CO)CNR)(μ‐Cl)}2] and NN ligands. Their interionic structure in CD2Cl2 was determined by means of 19F,1H‐HOESY experiments and compared with that in the solid state derived from X‐ray single‐crystal studies. [Pd(C6H4(C6H5CO)CNR)(NN)] [X] complexes were found to copolymerize CO and p‐methylstyrene affording syndiotactic or isotactic copolymers when bpy or 1,4‐(o,o′‐dimethylaryl)‐1,4‐diazabuta‐1,3‐dienes were used, respectively. The reactions with CO and p‐methylstyrene of the bpy derivatives were investigated. Two intermediates derived from a single and a double insertion of CO into the PdC bonds were isolated and completely characterized in solution.
ISSN:0018-019X
1522-2675
DOI:10.1002/hlca.200690155