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Selectivity in reductive elimination and organohalide transfer from methyl(aryl)benzylpalladium(IV) complexes of bidentate nitrogen donor ligands, PdBrMe(Ar)(CH2Ph)(L2)

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Kruis, D, Markies, BA, Canty, AJ, Boersma, J and van Koten, G 1997 , 'Selectivity in reductive elimination and organohalide transfer from methyl(aryl)benzylpalladium(IV) complexes of bidentate nitrogen donor ligands, PdBrMe(Ar)(CH2Ph)(L2)' , Journal of Organometallic Chemistry, vol. 532, no. 1-2 , pp. 235-242 , doi: 10.1016/S0022-328X(96)06795-2.

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Abstract

Oxidadve addiion of iodoarenes to bis(dibenzylideneacetone)palladium(0) in the presence of N.N. N’,N’-tetramethylethylenediamine (tmeda) affords PdIAr(tmeda) (Ar = 4-MeC6H4, 4-MeOC6H4, 4-Me(O)C6H4, 4-O2NC6H4, 3-MeOC6H4) in high yield. Some of these complexes (Ar = 4-MeC6H4, 4-MeOC6H4, 3-MeOC6H4) react with LiMe to form PdMeAr(tmeda), and the methyl(aryl)palladium(II) complexes react wbb 2,2’-bipyridyl (bpy) or 1,10-phenanthroline (phen) to afford PdMeAr(L2): PdMePh(phen) may be obtained similarly. All of the diorganopalladium(II) complexes of bpy and phen react with benzyl bromide to form PdBrMeAr(CH2Ph)(L2) but a complex could not be isolated for Ar = 3-MeOC6H4, L2 = bpy. The isolated palladium(IV) complexes react wbh PdMe2(bpy) at -20°C in (CD3)2C0 to selectively transfer henzy1 bromide to give PdMeAr(L2) and PdBrMe2(CH2Ph)(bpy) respctively. The complexes PdBrMeAr(CH2Ph)(bpy) (Ar = Pb, 4-MeC6H4. 4MeOC6H4) undergo selective reductive elimination of Ar-Me in CDCl3 to form PdBr(CH2Ph)(L2), but PdBrMeAr(CH2Ph)(phen) (Ar = Ph. 4-MeC6H4, 4-MeOC6H4, 3-MeOC6H4) give mixtures of PdBr(CH2Ph)(phen) and Me-Ar togaher with lesser amounts of PdBrMe(phen) and Ar-CH2Ph (ca. 10-20%).

Item Type: Article
Authors/Creators:Kruis, D and Markies, BA and Canty, AJ and Boersma, J and van Koten, G
Journal or Publication Title: Journal of Organometallic Chemistry
ISSN: 0022-328X
DOI / ID Number: 10.1016/S0022-328X(96)06795-2
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