Bis benzonitrile dichloropalladium II

Solubility soluble in acetone, chloroform, dichloromethane, benzene, toluene, CH3CN, THF, dioxane, DMF, DMF, etc. 

Form Supplied in commercially available as an orange-yellow powder 

Preparative Methods Palladium chloride was dissolved in a minimum volume of benzonitrile by heating to 100 °C. Then the solution was filtered, cooled, and diluted with petroleum ether with a low-boiling point. After washing with the same solvent, the combined precipitates were dried under vacuum (9-10 mm Hg) for one hour to afford the title complex in about 90% yield.  

General Considerations. The title reagent is most often used as a soluble source of palladium chloride. Reactions of this and other palladium chloride derivatives are descrihed in the article on palladium(II) chloride. The title reagent is most often used as a Pd catalyst. 

Shanghai Institute of Organic Chemistry, Shanghai, China 

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Ethyl diphenylphosphinite, 131 Hexamethyldisilazane, 141 Thionyl chloride, 297 Zirconium(IV) acetylacetonate, 351 From other starting materials Acetohydroxamic acid, 2 Bis(benzonitrile)dichloropalladium(II), 34... 

Carboxyethylthio aryl tellurium compounds displaced benzonitrile in bis[benzonitrile] dichloropalladium(II)5. 

Phenyl triphenylgermyl or triphenylstannyl tellurium transferred the benzenetellurolate group to palladium in a reaction with bis[benzonitrile]dichloropalladium(II)1. 

The formation of (l,5-hexadiene)dichloropalladium(II) by reaction of dry allyl chloride with bis(benzonitrile)dichloropalladium(II) at about 5°C has been reported (627). X-Ray analysis has shown the molecule to have the structure (200) in which carbon atoms C-1-C-2-C-3 and C-4-C-5-C-6 are in mutually perpendicular planes both of which are... 

Rearrangement of cis,reaction with bis(benzonitrile)dichloropalladium(II) in benzene has also been reported (581). The product is (m-l,2-divinylcyclohexane)dichloro-palladium(II), a monomeric complex decomposing above 123°C. The... 

Interaction of bis(benzonitrile)dichloropalladium(II) with all-trans-and cis,trows,melting with decomposition at 170° and 190°C, respectively. The infrared spectra of the complexes indicate that coordination is at a trans double bond in both species. 

The reaction of 13x with bis(benzonitrile)dichloropalladium(II) [Bn2PdCl2[ and monochloro(l,5-cyclooctadiene)monomethylpalladium(ll) [(COD)PdCIMe] yielded the corresponding palladium(II) complexes 14x and 15x (Fig. 2.16). Upon slow evaporation of an acetonitrile solution, 14 c and 14 d gave crystals that were suitable for structure determination via single crystal X-ray diffraction (Fig. 2.17). Compound 14 b was crystallized by slow diffusion of pentane into a solution of 14b in tetrachloroethane. 

Bis(benzonitrile)dichloropalladium(II)18 (3.00 g., 7.8 mmoles) is dissolved in a mixture of 40 ml. of water and 60 ml. of acetone. trans, trans-2,4-Hexadiene (3.5 ml., 35 mmole) is added. After 10 minutes the solution is extracted with dichloromethane, and the extract is washed with water and dried over Na2S04. After evaporation to dryness, the residue is dissolved in a small amount (5-10 ml.) of CH2C12 and filtered. The filtrate is diluted with pentane until the solution becomes turbid and a precipitate appears. In addition, the solution is cooled to —80°. Filtration through a sintered-glass filter and drying under vacuum gives 1.5 g. (80% theoretical) of the title compound. 

A mixture of 1-naphthalenesulfonyl chloride, /i-butyl acrylate, K2CO3, and catalytic amounts of bis(benzonitrile)dichloropalladium(II) and benzyltrioctylammonium chloride in m-xylene stirred at 140° for 4 h under N2 butyl 3-(l-naphthyl)-2-prope-noate. Y 90%. F.e.s. M. Miura et al.. Tetrahedron Letters 30, 975-6 (1989). 

The only stable Pd(II) compound with bis(/ r/-butyl)acetylene may be prepared by reaction of Bu CCBu with bis(benzonitrile)dichloropalladium(II) or di-/x-chloro-dichlorodi (ethylene )dipalladium (II) ... 

Formation of Isocyanates. The Pd-catalyzed reaction of PhI=NS02Ar in the presence of CO generates the isocyanates ArS02NC0. Thus bis(benzonitrile)dichloropalladium(II) catalyzes the formation of the isocyanate TsNCO (which can be isolated as the urea 6 in 60% 3deld after reaction with 2-chloroaniline) with PhI=NTs (eq 18). This reaction has been reported for several arylsulfonylimino iodinanes. Similar results can be achieved, however, by emplo3dng the less expensive chloramine-T and its derivatives as reagents. ... 

When bis(benzonitrile)dichloropalladium(II) is employed instead of Pd(OAc)2, terminal alkynes undergo Markovnikov addition of benzenethiol and double-bond isomerization sequentially to provide the corresponding internal vinylic sulfides in good yields (Scheme 14). ... 

Pd(0) Generation In Situ. Although used less extensively as a Pd(0) precursor than palladium(II) acetate, PdBr2 has been utilized in this role likewise to palladium(II) chloride and bis(benzonitrile)dichloropalladium(II). 

General Considerations. Many of the reactions described below can be accomplished using derivatives of palladium chloride such as potassium tetrachloropaUadate(II), disodium tetra-chloropalladate(II), Bis(benzonitrile)dichloropalladium(II), dichlorobis(acetonitrile)palladium, and dichloro-... 

Shengming Ma Shanghai Institute of Organic Chemistry, Shanghai, China Bis(benzonitrile)dichloropalladium(II) 66... 

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