Synthesis, Structural Preference and Catalytic Activity of Neutral and Cationic Methylpalladium(II) Complexes Containing N-Arylpyridine-2-carbaldimine Chelating Ligands

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Title:Synthesis, Structural Preference and Catalytic Activity of Neutral and Cationic Methylpalladium(II) Complexes Containing N-Arylpyridine-2-carbaldimine Chelating Ligands
Creators:
Arnaiz, Ana
García-Herbosa, Gabriel
Cuevas, José V.
Lavastre, Olivier
Hillairet, Caroline
Toupet, Loïc
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 67, 8, pp. 1200-1214
Uncontrolled Keywords:Ethylene, X-Ray diffraction, Chelates, Oligomerization, DFT calculations, Isomeric preference, Homogeneous catalysis, Carbon monoxide, Imines, Palladium

Abstract

The syntheses and structures of neutral complexes [PdCl(Py-2-CH=NAr)(Me)] (Ar = 4-MeC<sub>6</sub>H<sub>4</sub>, 4-MeOC<sub>6</sub>H<sub>4</sub>, 4-CF<sub>3</sub>C<sub>6</sub>H<sub>4</sub>) and cationic complexes [Pd(Py-2-CH=NAr)(Me)(MeCN)]SbF<sub>6</sub> (Ar = 4-MeC<sub>6</sub>H<sub>4</sub>, 4-MeOC<sub>6</sub>H<sub>4</sub>, 4-CF<sub>3</sub>C<sub>6</sub>H<sub>4</sub>) are described. The preference for the <i>trans</i>-isomers in the cationic complexes and for the <i>cis</i>-isomers in the neutral complexes is discussed on the basis of electronic arguments and supported by DFT calculations. The observed preference seems to follow the maximum hardness principle (MHP) introduced by Pearson. On the basis of the application of this principle to square planar complexes of palladium(II) and platinum(II) we propose the <i>trans choice</i>, which means that the hardest ligand arranges <i>trans</i> to the softest one. The synthesis and crystal structure of the related neutral complex <i>trans</i>-[Pd(CF<sub>3</sub>COO)(Py-2-CH=NC<sub>6</sub>H<sub>4</sub>-4-OMe)(Me)] is also described and allows to rule out the charge of the complex as the cause of isomeric preference. We also report our preliminary studies dealing with the catalytic activity of the cationic complexes in alkene oligomerization and copolymerization with CO. <p>

Title:Synthesis, Structural Preference and Catalytic Activity of Neutral and Cationic Methylpalladium(II) Complexes Containing N-Arylpyridine-2-carbaldimine Chelating Ligands
Creators:
Arnaiz, Ana
García-Herbosa, Gabriel
Cuevas, José V.
Lavastre, Olivier
Hillairet, Caroline
Toupet, Loïc
Uncontrolled Keywords:Ethylene, X-Ray diffraction, Chelates, Oligomerization, DFT calculations, Isomeric preference, Homogeneous catalysis, Carbon monoxide, Imines, Palladium
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:67
Number:8
Page Range:pp. 1200-1214
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20021200UNSPECIFIED
ID Code:1984
Item Type:Article
Deposited On:06 Feb 2009 17:14
Last Modified:06 Feb 2009 16:14

Citation

Arnaiz, Ana; García-Herbosa, Gabriel; Cuevas, José V.; Lavastre, Olivier; Hillairet, Caroline; Toupet, Loïc (2002) Synthesis, Structural Preference and Catalytic Activity of Neutral and Cationic Methylpalladium(II) Complexes Containing N-Arylpyridine-2-carbaldimine Chelating Ligands. Collection of Czechoslovak Chemical Communications, 67 (8). pp. 1200-1214. ISSN 0010-0765

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