Palladium dihalides

Mechanistically, all catalytic systems, including heterogeneous catalysts, pal-ladacydes and pincers operate through the formation of soluble Pd(0) nanoparticles in solution. In the catalytic cycle the aryl halide oxidatively adds to the palladium atoms at the rim, leading to the formation of an anionic aryl-palladium dihalide complex, or possibly its dimer. This anionic species then completes the Heck cycle. 

W-phosphinomethyl-NHC [45e], and W-phosphinoethyl-NHC [13a] platinum- or palladium dihalide model complexes (below, hydrogen atoms omitted for clarity). 

Preparation of the substituted piperazine required for sul-falene (114) starts with bromination of 2-aminopiperazine to give the dihalide (150). Displacement of halogen by sodium methoxide proceeds regioselectively at the more reactive 3 position to give 151. Hydrogenolysis over palladium on charcoal gives the desired intermediate (152). 

Geminal dihalides undergo partial or total reduction. The latter can be achieved by catalytic hydrogenation over platinum oxide [512], palladium [512] or Raney nickel [63, 512], Both partial and total reduction can be accomplished with lithium aluminum hydride [513], with sodium bis(2-meth-oxyethoxy)aluminum hydride [514], with tributylstannane [503, 514], electro-lytically [515], with sodium in alcohol [516] and with chromous sulfate [193, 197]. For partial reduction only, sodium arsenite [220] or sodium sulfite [254] are used. 

Trigeminal trihalides are completely reduced by catalytic hydrogenation over palladium [62] and Raney nickel [63], and partially reduced to dihalides or monohalides by electrolysis using mercury cathode [57 ], by aluminum... 

When the metallic additive to the intermediate 374 was zinc dihalide (or another Lewis acid, such as aluminum trichloride, iron trichloride or boron trifluoride), a conjugate addition to electrophilic olefins affords 381 . In the case of the lithium-zinc transmetallation, a palladium-catalyzed Negishi cross-coupling reaction with aryl bromides or iodides allowed the preparation of arylated componnds 384 ° in 26-77% yield. In addition, a Sn2 allylation of the mentioned zinc intermediates with reagents of type R CH=CHCH(R )X (X = chlorine, bromine) gave the corresponding compounds 385 in 52-68% yield. ... 

Palladium-catalyzed a-arylation of ketones is performed with arylene dihalides and bifunctional aromatic ketones 148 to result in the bond formation at the r/) -a-carbon of the ketone, leading to polyketone 149. The reaction is carried out in the presence of Pd(0) and various phosphines. Several bidentate phosphines and bulky alkylphosphines such as dppf, BINAP, PCys, and P Bu3 are shown to be effective, while PPh3 results in no reaction. Arylene dibromide and diiodide are applicable as the co-monomers. The polymerization reaction is carried out in THE in the presence of NaO Bu at 75 °C under N2, and polymers 149 are isolated in 60-80% yields (M = 7000-15 000). Polyketone 149 is further transformed to conjugated polymer PPV by reduction of the ketone moiety with LiAlH4 followed by dehydration with an acid (Equation (69)). 

Ethylene is also employed as an olefmic component of the Mizoroki-Heck polymerization. Organic dihalides thus couple with ethylene in the presence of a palladium catalyst to afford PAV-type polymers 161 and 162, as shown in Equations (77) and (78). ... 

Tomita and Endo have shown that three-component coupling of bisallene 163, aryl dihalide, and a malonate nucleophile takes place with a palladium catalyst. Arylpalladium species derived from the halide attacks the central carbon of allene to form a Tt-allylpalladium intermediate, which is then attacked by the malonate anion to form C-C... 

The palladium-catalyzed amination reaction with a monofunctional primary amine 167 effects i / -diarylation to afford the tertiary amine polymers 168. Hence, polycondensation of 167 with bifunctional arylene dihalides leads to 168 (Equation (81)). Polycondensation of a primary amine bearing an azobenzene moiety with dibromides in the presence of Pd2(dba)3 (2.5mol%)- Bu3P (P/Pd = 3 l) and NaO Bu at 100°G for 24h in toluene gives 168 in 81-93% yields, as reported by Kanbara. 

The halides of the palladium and platinum groups of metals closely resemble in character those of gold, which have already been described. The dihalides of the palladium group are all soluble, save Pdl2, which is prepared by precipitation with potassium iodide. Nitro-hydro-chloric acid yields the higher chloride it remains on evapo-... 

Palladium(i).—Unusual carbonylhalide complexes of palladium(i), [PdX(CO)] (X = Cl or Br), have been isolated by reduction of the dihalide with CO (equation 5).11... 

Fluoride derivatives of palladium(II) and platinum(II), all of which are phosphine derivatives, can be most simply grouped into one of two subsections, namely neutral or cationic species. The neutral species are all of the form [MXF(PPh3)2] (M = Pd, Pt) where X can be Cl, Br, I, H, methyl, phenyl and C6F5. The synthetic route into these compunds involves either addition of HF to a metal phosphine dihalide or... 

Finally, hydrogenolysis of the halogen atom of a-halocarbonyl compounds can be carried out at noble metal catalysts. Palladium is frequently used for this purpose. Selective removal of just one of the halogen atoms in the dihalides (32) can be effected in NaOAc/HOAc over a palladium catalyst. ... 

The simplest catalyst precursors are the metal dihalides. A number of routes have been developed into these and other catalyst precursors. These methods and the routes to particular complexes of nickel and palladium bearing a-diimine ligands are summarized in Table 1.91107-112 easiest involve... 

The Vcp couplings have been measured by Marinic et al for diethyl 2- and 8-quinolylmethylphosphonates and their palladium(II) dihalide complexes, trans-[PdL2X2], X = Cl, Br in the ligands additionally the C-P couplings across four and five bonds have been observed. 

---