Effect of Ligand Steric Properties and Halide Identity on the Mechanism for Oxidative Addition of Haloarenes to Trialkylphosphine Pd(0) Complexes

被引:219
作者
Barrios-Landeros, Fabiola [2 ]
Carrow, Brad P. [1 ]
Hartwig, John F. [1 ]
机构
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
[2] Yale Univ, Dept Chem, New Haven, CT 06520 USA
关键词
PALLADIUM-CATALYZED AMINATION; ARYL HALIDES; REDUCTIVE ELIMINATION; ZEROVALENT PALLADIUM; COUPLING REACTIONS; ROOM-TEMPERATURE; AROMATIC IODIDES; HECK REACTION; PHOSPHINE; CHLORIDES;
D O I
10.1021/ja900798s
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The oxidative addition of PhX (X = I, Br, Cl) to the complexes Pd(PtBu3)(2) (1), Pd(1-AdP(t)Bu(2))(2) (2), Pd((CyPBu2)-Bu-t)(2) (3), and Pd(PCy3)(2) (4) (1-Ad = 1-adamantyl, Cy = cyclohexyl) was studied to determine the effect of steric properties on the coordination number of the species that undergoes oxidative addition and to determine whether the type of halide affects the identity of this species. The kinetic data imply that the number of phosphines coordinated to the complex that reacts in the irreversible step of the oxidative addition process for complexes 1-4 depends more on the halide than on the steric properties of the ligands. The rate-limiting step of the oxidative addition of PhI occurred with L2Pd(0) in all cases, as determined by the lack of dependence of k(obs) on [(PBu3)-Bu-t], [1-AdP(t)Bu(2)], or [(CyPBu2)-Bu-t] and the inverse dependence of the rate constant on [PCy3] when the reaction was initiated with Pd(PCy3)(3). The irreversible step of the oxidative addition of PhCl occurred with a monophosphine species in each case, as signaled by an inverse dependence of the rate-constant on the concentration of ligand. The irreversible step of the oxidative addition of PhBr occurred with a bisphosphine species, as signaled by the zeroth-order or small dependence of the rate constant on the concentration of phosphine. Thus, the additions of the less reactive chloroarenes occur through lower-coordinate intermediates than additions of the more reactive haloarenes.
引用
收藏
页码:8141 / 8154
页数:14
相关论文
共 50 条
[21]   OXIDATIVE ADDITION OF ARYL BROMIDE AFTER DISSOCIATION OF PHOSPHINE FROM A 2-COORDINATE PALLADIUM(0) COMPLEX, BIS(TRI-O-TOLYLPHOSPHINE)PALLADIUM(0) [J].
HARTWIG, JF ;
PAUL, F .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (19) :5373-5374
[22]   Room-temperature palladium-catalyzed amination of aryl bromides and chlorides and extended scope of aromatic C-N bond formation with a commercial ligand [J].
Hartwig, JF ;
Kawatsura, M ;
Hauck, SI ;
Shaughnessy, KH ;
Alcazar-Roman, LM .
JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (15) :5575-5580
[23]  
Herrmann W.A., 2002, APPL HOMOG CATAL ORG, V1, P591
[24]  
Huser M., 1989, Angewandte Chemie International Edition, V101, P1427
[25]   DFT studies on the effect of the nature of the aryl halide Y-C6H4-X on the mechanism of its oxidative addition to Pd0L versus Pd0L2 [J].
Lam, King Chung ;
Marder, Todd B. ;
Lin, Zhenyang .
ORGANOMETALLICS, 2007, 26 (03) :758-760
[26]   Synthetic, structural, and mechanistic studies on the oxidative addition of aromatic chlorides to a palladium (N-heterocyclic carbene) complex:: Relevance to catalytic amination [J].
Lewis, AKD ;
Caddick, S ;
Cloke, FGN ;
Billingham, NC ;
Hitchcock, PB ;
Leonard, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (33) :10066-10073
[27]  
Littke AF, 2002, ANGEW CHEM INT EDIT, V41, P4176, DOI 10.1002/1521-3773(20021115)41:22<4176::AID-ANIE4176>3.0.CO
[28]  
2-U
[29]   The F/Ph rearrangement reaction of [(Ph3P)3RhF], the fluoride congener of Wilkinson's catalyst [J].
Macgregor, SA ;
Roe, DC ;
Marshall, WJ ;
Bloch, KM ;
Bakhmutov, VI ;
Grushin, VV .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (43) :15304-15321
[30]   PHOSPHORUS-31 NUCLEAR MAGNETIC-RESONANCE SPECTROSCOPIC CHARACTERIZATION OF TERTIARY PHOSPHINE PALLADIUM(0) COMPLEXES - EVIDENCE FOR 14-ELECTRON COMPLEXES IN SOLUTION [J].
MANN, BE ;
MUSCO, A .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1975, (16-1) :1673-1677