Insights into amine binding to biaryl phosphine palladium oxidative addition complexes and reductive elimination from biaryl phosphine arylpalladium amido complexes via density functional theory

被引:144
作者
Barder, Timothy E. [1 ]
Buchwald, Stephen L. [1 ]
机构
[1] MIT, Dept Chem, Cambridge, MA 02139 USA
关键词
D O I
10.1021/ja073747z
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We present results on the binding of a variety amines to monoligated oxidative addition complexes of the type L1Pd(Ar)Cl, where L is 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos, 1) or 2-dicyclohexylphosphino-2',4',6'-tri-ispropylbiphenyl (XPhos, 2). The binding of an amine to oxidative addition complexes composed of 1 and 2 is more complex than with smaller ligands as intermediate Pd(l I) complexes with bulky biaryl phosphine ligands disfavor amine binding to favorable conformations of oxidative addition complexes. Additionally, thermodynamic and kinetic parameters for reductive elimination from complexes of the type L,Pd(amido)Ph (where amido = EtNH, Me2N, PhNH) are discussed. From this data, we suggest a possible mechanism for (biaryl phosphine) Pd-catalyzed amination reactions that is more intricate than previously thought.
引用
收藏
页码:12003 / 12010
页数:8
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