The synthesis of C-2 cyclopalladated derivatives of 1,3-bis(2-pyridyl)benzene (N-CH-N) has been achieved for the first time through a transmetalation reaction. C-2 mono- and dinuclear complexes have been obtained by reaction of Pd(OAc)(2) and the organomercury(H) compound [Hg(N-C-N)Cl] (1) as precursors. The new species 2-11 were characterized in solution and, in the case of [Pd(N-C-N)Cl] (2) and [Pd-2(N-C-N)(2)(OAc)](2)[Hg2Cl6] (11) as well as of [Hg(N-C-N)Cl] (1), in the solid state. The X-ray crystal structures unambiguously show the pincer behavior of the N-C-N ligand in the palladium species and the linear coordination C-Hg-Cl in the mercury precursor. Displacement of the coordinated halide gives cationic species such as [Pd(N-C-N)(H2O)][BF4] (5) or, in the absence of donor solvents or anions, the dinuclear halide-bridged species [Pd-2(N-C-N)(2)(mu-X)][BAr'(4)] (X = Cl (6), Br (7), I (8); Ar' = 3,5-(CF3)(2)-C6H3). For comparison purposes [Pd(N-C-N)(OAc)] (9) and [Pd-2(N-C-N)(2)(mu-OAc)][BAr'(4)] (10) were also prepared. The mononuclear complexes 2, 4, 5, and 9 are high-performance catalysts in the Heck reaction of iodobenzene and methyl acrylate, even at moderate temperatures. Under microwave heating a turnover frequency as high as 280 000 h(-1) is observed with complex 2 at the nominal temperature of 135 degreesC.
|Titolo:||Synthesis of the first C-2 cyclopalladated derivatives of 1,3-bis(2-pyridyl)benzene. Crystal structures of [Hg(N-C-N)Cl], [Pd(N-C-N)Cl], and [Pd-2(N-C-N)(2)(mu-OAc)](2)[Hg2Cl6]. Catalytic activity in the heck reaction|
MANASSERO, MARIO (Penultimo)
SANSONI, MIRELLA (Ultimo)
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||2005|
|Digital Object Identifier (DOI):||10.1021/om040102o|
|Appare nelle tipologie:||01 - Articolo su periodico|