17830-50-1

Upstream product

• 78192-91-3 [N,N′-1,2-ethanediylidenebis[2-methyl-2-propanamine-κN]][(3,4-η)-2,5-furandione]-palladium 
• 603-35-0 triphenylphosphine 
• 108-31-6 maleic anhydride 
• 34772-26-4 {((C₆H₅)3P)3PdCl}⁽¹⁺⁾*BF₄^(1-)={((C₆H₅)3P)3PdCl}BF₄ 
• 7732-18-5 water 

Relevant academic research and scientific papers

C-C reductive elimination in palladium complexes, and the role of coupling additives. A DFT study supported by experiment

A DFT study of R-R reductive elimination (R = Me, Ph, vinyl) in plausible intermediates of Pd-catalyzed processes is reported. These include the square-planar tetracoordinated systems cis- [PdR2 (PMe 3)2] themselves, possi

Palladium(0)-alkene bis(triarylphosphine) complexes as catalyst precursors for the methoxycarbonylation of styrene

The fluorous complex [Pd(0)(P{C6H4-p-SiMe 2(CH2CH2C6F13)} 3)2(MA)] (MA = maleic anhydride) was synthesized and characterized by its NMR spectra. Together with the nonfluorous complexes [Pd(0)(PPh3)2(alkene)] (alkene = C2H 4) (NC)2C=C(CN)2), NCC(H)= C(H)CN, MA, or benzoquinone) these were evaluated as catalyst precursors in the methoxycarbonylation of styrene. The nonfluorous C2H4 and MA complexes gave the highest conversions (the turnover number (TON) was 120; the (average) turnover frequency (TOF) amounted to 80 h-1). The fluorous complex gave a significantly lower conversion (TON about 38; TOF 26 h-1) than its nonfluorous counterpart, which is caused by a lower stability of the fluorous complex under the reaction conditions.

Fluoride-induced reduction of palladium(II) and platinum(II) phosphine complexes

A novel redox reaction involving fluoride and phosphine complexes of palladium(II) is reported. The scope of this reaction has been investigated using the ligands PPh3, Ph2P(CH2)nPPh2 (n = 1-4), Ph2PCH2C(CH3)2CH2PPh 2, Ph2PCH3, and P(CH2CH2CN)3; several solvents including DMSO, pyridine, acetonitrile, and THF; and either n-Bu4NF·3H2O or KF/18-crown-6 as the fluoride source. The reduction products are palladium(0) phosphine complexes for which this reaction offers a convenient synthetic route. 31P and 19F NMR spectra permitted identification of the initial oxidation products as difluorophosphoranes (R3PF2), which subsequently hydrolyzed, forming phosphine oxides if a hydrated fluoride source is used. Results implicating a fluoride-induced redox reaction in the thermal decomposition of [(Ph3P)3PdCl]BF4 to yield [Pd3Cl(PPh2)2(PPh3) 3]BF4 are also presented. Preliminary results indicate that platinum complexes also undergo this reaction, but nickel complexes yield NiF2. The X-ray parameters for Pd(dppp)2 (dppp = 1,3-bis(diphenyphosphino)propane) are: monoclinic, space group C2/c (No. 15), a = 18.396 (2) A?, b = 13.290 (1) A?, c = 20.186 (2) A?, β = 109.383 (5)°, and Z = 4.

Palladium- or Nickel-Catalyzed Reactions of Alkenylmetals with Unsaturated Organic Halides as a Selective Route to Arylated Alkenes and Conjugated Dienes: Scope, Limitations, and Mechanism

Stereo- and regiodefined alkenylmetals containing Al, Zr, and Zn react with aryl and alkenyl iodides and bromides in the presence of catalytic amounts of Pd or Ni complexes containing phosphine ligands, such as PPh3, to give the corresponding cross-coupled products.Palladium catalysts permit nearly 100 percent stereospecificity in both alkenyl-aryl and alkenyl-alkenyl coupling reactions, whereas nickel catalysts lead to partial stereochemical scrambling in the alkenyl-alkenyl coupling.Although many other metals including Li, Mg, Cd, Hg, B, Si, Sn, Ti, and Ce were also used, the results were inferior to those obtained with Al, Zr, and Zn under the conditions used in the present study.The turnover numbers for the palladium-catalyzed reactions of PhI with (E)-1-octenylmetals containing Al, Zr, and Zn were 2,3, and > 2000 mmol of (E)-1-octenylbenzene (8) per mmol of Pd(PPh3)4 per hour at room temperature, respectively.The stoichiometric reaction of PhPd(PPh3)2I (6) with 1.2 equiv of (E)-1-octenylzinc chloride (7) in a 2:1 mixture of CD2Cl2 and THF was examined in detail.The reaction follows second-order konetics (k2 = 2.9 L/(mol.min) at 0 deg C) to give 8 without the buildup of any intermediate.The results are consistent with a slow formation of 9 via transmetalation followed by its rapid reductive elmination to give 8 and "Pd(PPhe3)2".Addition of PhI to the reaction mixture rapidly gives 6 in 98 percent yield, supporting the plausibility of the proposed oxidative addition step.These results are consistent with the proposed mechanism consisting of oxidative addition of Pd(0) complexes, rate-determining transmetalation involving Pd(II) complexes, and rapid decomposition of diorganopalladium(II) species to produce the coupling products in one or more subsequent steps.The rate-determining transmetalation step provides an explanation for the effect of metals in organometallic reagents used stoichiometrically.