1287312-89-3

Upstream product

• 3375-31-3 palladium diacetate 
• 1439-43-6 1-(4-nitro-phenyl)-2-(triphenyl-λ⁵-phosphanylidene)-ethanone 
• 7647-14-5 sodium chloride 

Downstream Products

• 1286835-58-2 [Pd(bis(diphenylphosphino)propane)(κ2(C,C)-C6H4PPh2CHC(O)C6H4NO2)](trifluoromethylsulfonate) 
• 1286835-54-8 [Pd(2,2'-bipyridine)(κ2(C,C)-C6H4PPh2CHC(O)C6H4NO2)](trifluoromethylsulfonate) 
• 1286835-52-6 [Pd(1,10-phenanthroline)(κ2(C,C)-C6H4PPh2CHC(O)C6H4NO2)](trifluoromethylsulfonate) 
• 1286835-56-0 [Pd(bis(diphenylphosphino)ethane)(κ2(C,C)-C6H4PPh2CHC(O)C6H4NO2)](trifluoromethylsulfonate) 

Relevant academic research and scientific papers

Synthesis, structural and theoretical studies of Pd(II) complexes containing an orthometallated C, C-chelating phosphorus ylide

The phosphorus ylide [Ph3PCHC(O)C6H 4-NO2-4] (1) reacted with Pd(OAc)2 to give the C, C-orthometallated complexes [Pd{K2(C, C)-C6H 4PPh2C(H)CO(C6H4-NO2-4)}(μ-X)] 2 (X = Cl (2); X = Br (3)) as a mixture of isomers, which underwent bridge cleavage reactions with monodentate ligands to afford the monomeric, neutral Pd(II) complexes [Pd{κ2(C, C)-C6H 4PPh2C(H)CO(C6H4-NO 2-4)}X(L)] (X = Cl, L=Me3Py (4), PPh3 (5); X = Br, L = Me3Py (6), 4-MePy (7), PPh3 (8). The complexes were identified and characterized by spectroscopic studies (IR and NMR). The X-ray single crystal analysis of 6 and 7 revealed the presence of an orthometallated C6H4-2-PPh2 unit and a C-linked ylide, Pd-C(H). In the crystal structure of 6, the location of the Me3Py ligand is trans to the Pd-Cylide, according to the anti-symbiotic effect, whereas in 7 the 4-MePy ligand is preferentially cis to the Pd-Cylide. Density functional theory (DFT) calculations in the reaction solvent (dichloromethane) indicated that the trans isomers of 6 and 7 are 3.03 and 0.70 kcal/mol more stable than their cis isomers, respectively.

Orthopalladation of phosphorus ylides in endo position with bidentate ligands

The ortho-metallated complexes [Pd2{κ2(C,C)- C6H4(PPh2CHC(O)C6H 5R}2(μ-Cl)2] (R = Ph (1a), NO2 (1b), Br (1c)) were prepared by refluxing equimolar mixtures of Ph 3PCHC(O)C6H5R, (R = Ph, NO2, Br) and Pd(OAc)2 in MeOH, followed by an excess of NaCl. The dinuclear complexes (1a-1c) react with silver trifluoromethylsulfonate and bidentate ligands [L = bipy (2,2′-bipyridine), phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), dppp (bis(diphenylphosphino)propane)] giving the mononuclear stabilized orthopalladated complexes in endo position [Pd{κ2(C,C)-C6H4(PPh2CHC(O)R} L](OTf) [R = Ph, L = phen (2a), bipy (3a), dppe (4a), dppp (5a); R = NO 2, L = phen (2b), bipy (3b), dppe (4b), dppp (5b); R = Br, L = phen (2c), bipy (3c), dppe (4c), dppp (5c); OTf = trifluoromethylsulfonate anion]. Orthometalation and ylidic C-coordination are demonstrated by an X-ray diffraction study of 2c and 3c. In the structures, the palladium atom shows a slightly distorted square-planar coordination geometry.