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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)(L-2)

Citation

Kruis, D and Markies, BA and Canty, AJ and Boersma, K and van Koten, G, Selectivity in reductive elimination and organohalide transfer from methyl(aryl)benzylpalladium(IV) complexes of bidentate nitrogen donor ligands, PdBrMe(Ar)(CH2Ph)(L-2), Journal of Organometallic Chemistry, 532, (1-2) pp. 235-242. ISSN 0022-328X (1997) [Refereed Article]

DOI: doi:10.1016/S0022-328X(96)06795-2

Abstract

Oxidative addition 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)CC6H4, 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 with 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 with PdMe2(bpy) at -20°C in (CD3)2CO to selectively transfer benzyl bromide to give PdMeAr(L2) and PdBrMe2(CH2PhXbpy) respectively. The complexes PdBrMeAr(CH2Ph)(bpy) (Ar = Ph, 4-MeC6H4, 4-MeOC6H4) 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 together with lesser amounts of PdBrMe(phen) and Ar-CH2Ph (ca. 10-20%).

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Canty, AJ (Professor Allan Canty)
ID Code:11867
Year Published:1997
Web of Science® Times Cited:30
Deposited By:Chemistry
Deposited On:1997-08-01
Last Modified:2011-08-12
Downloads:0

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