- Oxidative Addition of Aryl Sulfonates to Palladium (0) Complexes of Mono- and Bidentate Phosphines. Mild Addition of Aryl Tosylates and the Effects of Anions on Rate and Mechanism
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An analysis of the oxidative additions of aryl triflates to palladium(O) complexes of hindered mono and bis(phosphines) and aryl tosylates to palladium(O) complexes of bis(phosphines) are discussed. In the presence added halides reaction of Pd[P(o-tolyl)
- Roy, Amy H.,Hartwig, John F.
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p. 194 - 202
(2008/10/09)
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- Synthesis and solution structure of palladium tris(o-tolyl)phosphine mono(amine) complexes
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The complex(es) resulting from a 1:4 mixture Of Pd2(DBA)3 and P(o-tol)3 react with aryl bromides or aryl iodides p-XC6H4R (X = Br, I; R = Me, t-Bu, OMe) to generate the corresponding halide dimers {Pd[P(o-tol)3](p-C6H4R)(μ-X)}2 (X = Br, R = t-Bu (1), Me (2), OMe (3); X = I, R = t-Bu (4), Me (5), OMe (6)) in 46-76% yield. Iodide dimer 5 reacts with AgOTf in acetonitrile to form the cationic bis(acetonitrile) complex {Pd[P(o-tol)3](p-C6H4-Me)(CH 3CN)2]}+OTf- (8) which was treated in situ with LiCl to form the chloride dimer {Pd[P(o-tol)3](p-C6H4Me)(μ-Cl)}2 (9) in 93% yield. The p-tolyl halide dimers 2, 5, and 9 react with N-benzylmethylamine to generate the corresponding 1:1 palladium amine adducts Pd[P(o-tol)3](p-C6H4Me)[HN(Me)Bn]X (X - Cl (12), 85%; X = Br (13), 72%; X = I (14), 77%). Reaction of a mixture of Pd2(DBA)3 and P(o-tol)3 with the haloamines 2-IC6H4(CH2)2N(H)Bn, 2-BrC6H4CH2N(H)(p-tolyl), and 2-BrC6H4(CH2)3N(H)Bn gave the chelated palladium amine complexes Pd[P(o-tol)3](2-C6H4(CH2) 2N(H)Bn]I (18, 71%), Pd[P(o-tol)3][2-C6H4CH 2N(H)(p-tolyl)]Br (19, 77%), and Pd[P(o-tol)3](2-C6H4(CH2) 3N(H)Bn]Br (21, 24%), respectively. Variable-temperature 1H and 31P NMR analysis of 12-14 and related complexes was consistent with hindered rotation about the P-C bonds, with predominant formation of the exo2-P(o-tol) conformer, and hindered rotation about the Pd-P bond with formation of three unequally populated rotamers.
- Widenhoefer, Ross A.,Zhong, H. Annita,Buchwald, Stephen L.
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p. 2745 - 2754
(2008/10/08)
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