کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1324809 | 977356 | 2008 | 14 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Phosphite ligands derived from distally and proximally substituted dipropyloxy calix[4]arenes and their palladium complexes: Solution dynamics, solid-state structures and catalysis Phosphite ligands derived from distally and proximally substituted dipropyloxy calix[4]arenes and their palladium complexes: Solution dynamics, solid-state structures and catalysis](/preview/png/1324809.png)
Two bisphosphite ligands, 25,27-bis-(2,2′-biphenyldioxyphosphinoxy)-26,28-dipropyloxy-p-tert-butyl calix[4]arene (3) and 25,26-bis-(2,2′-biphenyldioxyphosphinoxy)-27,28-dipropyloxy-p-tert-butyl calix[4]arene (4) and two monophosphite ligands, 25-hydroxy-27-(2,2′-biphenyldioxyphosphinoxy)-26,28-dipropyloxy-p-tert-butyl calix[4]arene (5) and 25-hydroxy-26-(2,2′-biphenyldioxyphosphinoxy)-27,28-dipropyloxy- p-tert-butyl calix[4]arene (6) have been synthesized. Treatment of (allyl) palladium precursors [(η3-1,3-R,R′-C3H4)Pd(Cl)]2 with ligand 3 in the presence of NH4PF6 gives a series of cationic allyl palladium complexes (3a–3d). Neutral allyl complexes (3e–3g) are obtained by the treatment of the allyl palladium precursors with ligand 3 in the absence of NH4PF6. The cationic allyl complexes [(η3-C3H5)Pd(4)]PF6 (4a) and [(η3-Ph2C3H3)Pd(4)]PF6 (4b) have been synthesized from the proximally (1,2-) substituted bisphosphite ligand 4. Treatment of ligand 4 with [Pd(COD)Cl2] gives the palladium dichloride complex, [PdCl2(4)] (4c). The solid-state structures of [{(η3-1-CH3-C3H4)Pd(Cl)}2(3)] (3f) and [PdCl2(4)] (4c) have been determined by X-ray crystallography; the calixarene framework in 3f adopts the pinched cone conformation whereas in 4c, the conformation is in between that of cone and pinched cone. Solution dynamics of 3f has been studied in detail with the help of two-dimensional NMR spectroscopy.The solid-state structures of the monophosphite ligands 5 and 6 have also been determined; the calix[4]arene framework in both molecules adopts the cone conformation. Reaction of the monophosphite ligands (5, 6) with (allyl) palladium precursors, in the absence of NH4PF6, yield a series of neutral allyl palladium complexes (5a–5c; 6a–6d). Allyl palladium complexes of proximally substituted ligand 6 showed two diastereomers in solution owing to the inherently chiral calix[4]arene framework. Ligands 3, 6 and the allyl palladium complex 3f have been tested for catalytic activity in allylic alkylation reactions.
Selective phosphorus functionalization in the lower rim of distally and proximally substituted dipropyloxy calix[4]arenes with biphenyl-2,2′-dioxy moiety give two mono- and two bisphosphite ligands. Reactions of these ligands with palladium precursors give either bridged or chelated palladium complexes. The catalytic activity of one of the ligands and its palladium (methyl allyl) complex has been tested in allylic alkylation reaction.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 693, Issue 12, 1 June 2008, Pages 2097–2110