Quantitative synthesis and full characterization of the first isolated and stable pincer palladium(iv) complexes. Quantitative and regioselective synthesis of the C–X (X = Cl, Br) reductive elimination products
The pincer complexes [Pd(O(1),N(1),C(1)-L)X], where X = Cl, Br and L is the monoanionic ligand resulting from deprotonation of the acetyl methyl group of the monoketal of 2,6-diacetylpyridine (dap), react with excess of Cl(2) or Br(2) affording, quantitatively, the Pd(IV) complexes [Pd(O(1),N(1),C(1)-L)X(3)], which have been characterized by X-ray diffraction, and their decomposition that quantitatively
Four's a charm: Complex 1⋅OAc (see scheme) reacts with 2‐iodobenzoic acid to afford the stable PdIV complexes 2 a and 2 b. Complexes 2 are precatalysts for the orthovinylation of 2‐iodobenzoic acid with CH2CHCO2Me and AgClO4 at room temperature. The reaction is not quenched by excess Hg nor does it afford dibenzyl in the presence of benzyl chloride, suggesting that neither Pd nanoparticles nor a Pd0
Synthesis, Isolation, and Characterization of an Organometallic Triiodopalladium(IV) Complex. Quantitative and Regioselective Synthesis of Two C–I Reductive Elimination Products
Iodine and the pincer complex [Pd(O,N,C-L)I], where L is the monoanionic ligand resulting from deprotonation of the acetyl group of the dimethylmonoketal of 2,6-diacetylpyridine, are in equilibrium at low temperatures with the palladium(IV) complex [Pd(O,N,C-L)I-3], which can be isolated at -40 degrees C and characterized by H-1 NMR spectroscopy and X-ray diffraction studies, in spite of its great instability. When the same reaction is carried out at room temperature, a quantitative reductive elimination process occurs, giving L-I, which in the presence of water affords L'1, resulting from hydrolysis of L-I.