Synthesis and Characterization of Palladium Complexes Containing 3,3'-Annelated 2,2'-Bipyridines and 3,3'-Annelated 2,2'-Biquinolines

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Title:Synthesis and Characterization of Palladium Complexes Containing 3,3'-Annelated 2,2'-Bipyridines and 3,3'-Annelated 2,2'-Biquinolines
Creators:
Klein, René A.
Belzen, Ruud van
Vrieze, Kees
Elsevier, Cornelis J.
Thummel, Randolph P.
Fraanje, Jan
Goubitz, Kees
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 62, 2, pp. 238-256
Uncontrolled Keywords:Biquinoline, X-Ray crystallography, Bipyridine, Annelation, Palladium, Chirality

Abstract

The synthesis and characterization of a number of PdCl<sub>2</sub>(N⁀N) and Pd(N⁀N)(fn) complexes (N⁀N = 3,3'-annelated 2,2'-bipyridines and 3,3'-annelated 2,2'-biquinolines, fn = fumaronitrile) have been described. Despite the variation in dihedral angle and distance between the nitrogen lone pairs in these series of ligands, they are all capable of forming stable chelates. An investigation was made as to whether the 3,3'-trimethylene-2,2'-biquinoline (3-bq) and 3,3'-tetramethylene-2,2'-biquinoline (4-bq) ligands could serve as <i>C</i><sub>2</sub>-chiral auxiliaries. The ligand 3-bq in Pd(3-bq)(fn) turned out to be conformationally rigid on the NMR time scale, but the diastereomers appeared to be indistinguishable, as could be concluded from the <sup>1</sup>H NMR spectra. However, Pd(4-bq)(fn) exists in two diastereomeric forms and their ratio (57 : 43) could be determined from <sup>1</sup>H NMR spectra. Assignment of the major and minor isomers was done with a 2D NOESY experiment. Epimerization of the diastereomers occurred on the laboratory time scale which was deduced from a spin saturation transfer experiment and also from the observation that diastereomerically enriched crystalline material of Pd(4-bq)(fn) at low temperature showed a ratio of 80 : 20 which deteriorated to a ratio of 57 : 43. From the spin saturation transfer experiment, the thermodynamic parameters for the inversion could be determined (∆H<sup>≠</sup> = 29.1 kJ mol<sup>-1</sup> and ∆S<sup>≠</sup> = -136.3 J K<sup>-1 </sup>mol<sup>-1</sup>). This large negative entropy of activation favours an epimerization process <i>via</i> inversion of the coordinated 4-bq ligand over a mechanism <i>via</i> alkene dissociation/recoordination. The structures of the complexes have been studied in solution and in the solid state and the following X-ray crystal structures have been determined: (i) [dichloropalladium(II)](3,3'-trimethylene-2,2'-bipyridine-κ<sup>2</sup><i>N</i>), monoclinic crystals, space group <i>P2</i><sub>1</sub>/<i>n</i>, with <i>a</i> = 8.4230(7) Å, <i>b</i> = 16.425(2) Å, <i>c</i> = 9.5836(7) Å, β = 106.316(7)°, <i>Z</i> = 4, final <i>R</i> = 0.033 for 2 309 reflections, (ii) [3,3'-bis(methoxycarbonyl)-2,2'-bipyridine-κ<sup>2</sup><i>N</i>][dichloropalladium(II)], triclinic crystals, space group <i>P1</i>, with <i>a</i> = 7.340(4) Å, <i>b</i>= 10.012(3) Å, <i>c</i>= 11.954(3) Å, α = 98.10(2)°, β = 104.03(3)°, γ = 107.33(5)°, <i>Z</i> = 2, final <i>R</i> = 0.039 for 4 273 reflections, (iii) [chloromethylpalladium(II)](4,5-diazafluorene-κ<sup>2</sup><i>N</i>), orthorhombic crystals, space group <i>Pmcn</i>, with <i>a</i> = 6.713(1) Å, <i>b</i> = 10.120(1) Å, <i>c</i> = 17.187(3) Å, <i>Z</i> = 4, final <i>R</i> = 0.048 for 949 reflections.

Title:Synthesis and Characterization of Palladium Complexes Containing 3,3'-Annelated 2,2'-Bipyridines and 3,3'-Annelated 2,2'-Biquinolines
Creators:
Klein, René A.
Belzen, Ruud van
Vrieze, Kees
Elsevier, Cornelis J.
Thummel, Randolph P.
Fraanje, Jan
Goubitz, Kees
Uncontrolled Keywords:Biquinoline, X-Ray crystallography, Bipyridine, Annelation, Palladium, Chirality
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:62
Number:2
Page Range:pp. 238-256
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19970238UNSPECIFIED
ID Code:1111
Item Type:Article
Deposited On:06 Feb 2009 17:06
Last Modified:06 Feb 2009 16:06

Citation

Klein, René A.; Belzen, Ruud van; Vrieze, Kees; Elsevier, Cornelis J.; Thummel, Randolph P.; Fraanje, Jan; Goubitz, Kees (1997) Synthesis and Characterization of Palladium Complexes Containing 3,3'-Annelated 2,2'-Bipyridines and 3,3'-Annelated 2,2'-Biquinolines. Collection of Czechoslovak Chemical Communications, 62 (2). pp. 238-256. ISSN 0010-0765

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