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Synthesis and structural studies of phenyl(iodo)- and methyl(phenyl)palladium(II) complexes of bidentate nitrogen donor ligands


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Markies, BA, Canty, AJ, de Graaf, W, Boersma, J, Janssen, MD, Hogerheide, MP, Smeets, WJJ, Spek, AL and van Koten, G 1994 , 'Synthesis and structural studies of phenyl(iodo)- and methyl(phenyl)palladium(II) complexes of bidentate nitrogen donor ligands' , Journal of Organometallic Chemistry, vol. 482, no. 1-2 , pp. 191-199 , doi: 10.1016/0022-328X(94)88201-0.

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Phenylpalladium(II) complexes of the type PdIPh(N-N), with N-N = N,N,N’,N’-tetramethylethylenediamine (tmeda) or 2,2’-bipyridyl (bpy), can be conveniently prepared in 70-95% yield by oxidative addition of iodobenxene to bis(dibenzylideneacetone)palladium(0) in the presence of the appropriate nitrogen donor ligand. The bromo analogues were obtained in only 5-12% yield in this way. The complex PdIPh(tmeda) (la) reacts readily with MeLi to give PdMePh(tmeda) (3) in 88% yield, whereas PdIPh(bpy) (la) gives PdMePh(bpy) (4) and PdMe2(bpy) in varying ratios. The formation of PdMe2(bpy) was found to result from the
synergistic action of lithium iodide and methyllithium. Pure PdMePh(bpy) (4) was obtained in 82% yield via ligand-exchange from PdMePh(tmeda) (3). The crystal structures of PdIPh(N-N) (la, 2a) and PdMePh(N-N) (3, 4) complexes were determined by X-ray diffraction studies. The results show that the phenyl group is always oriented perpendicular to the coordination plane around palladium, with the largest deviation found for 3 (14.3(2)). The Pd-N bond distances in the tmeda complexes (2.127(6)-2.210(3) A) are larger than those in the bpy-coordinated complexes (2.870(8)-2.144(8) A). Similarly, the Pd-C(Me) bond distances (2.5703(8)
and 2.575(l) A) are larger than the Pd-C(Ph) bond distances (1.985(3)-1.996(lO) A).

Item Type: Article
Authors/Creators:Markies, BA and Canty, AJ and de Graaf, W and Boersma, J and Janssen, MD and Hogerheide, MP and Smeets, WJJ and Spek, AL and van Koten, G
Keywords: Palladium; Amine; Oxidative addition; Bipyridine; Crystal structure
Journal or Publication Title: Journal of Organometallic Chemistry
ISSN: 0022-328X
DOI / ID Number: 10.1016/0022-328X(94)88201-0
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