Palladium complexes, with

Reactions of zerovalent platinum and palladium complexes with organometallic compounds of nontransition metals. V. I. Sokolov and O. A. Reutov, Coord. Chem. Rev., 1978, 27, 89-107 (80). 

Cavell KJ, McGuinness DS (2007) Palladium complexes with carbonyl, isocyanide and carbene ligands. In Crabtree RH, Mingos DMP, Canty AJ (eds) Comprehensive organometallic chemistry 111. Elsevier, Amsterdam... 

Burgos, M., Crespo, O., Gimeno, M.C., Jones, P.G. and Laguna, A. (2003) Gold, silver and palladium complexes with the 2,2 -dipyridylamine ligand. European Journal of Inorganic Chemistry, (11), 2170-2174. 

NMR monitoring of the reaction of the palladium complex with 1-octyne suggested that the alkyne inserts into the Pd-H bond. Further heating produced a mixture of the two regioisomeric alkenylphosphine oxides, the anti-Markovnikov adduct being the favored product (54 46, 65% yield). 

Dixon, K. R. Dixon, A. C. Palladium Complexes with Carbonyl, Isocyanide and Carbene Ligands, In Comprehensive Organometallic Chemistry II A review of the literature 1982-1994 Puddephatt, R. J. Ed., Elsevier, 1995, Vol. 9, p 193. 

Helmchen and coworkers employed a,co-amino-1,3-dienes as substrates [51]. By using palladium complexes with chiral phosphino-oxazolines L as catalysts, an enantiomeric excess of up to 80 % was achieved. In a typical experiment, a suspension of Pd(OAc)2, the chiral ligand L, the aminodiene 6/1-90 and an aryltriflate in dimethylformamide (DMF) was heated at 100 °C for 10 days. Via the chiral palladium complex 6/1-91, the resulting cyclic amine derivative 6/1-92 was obtained in 47% yield and 80% ee (Scheme 6/1.23). Using aryliodides the reaction time is shorter, and the yield higher (61 %), but the enantiomeric excess is lower (67% ee). With BINAP as a chiral ligand for the Pd°-catalyzed transformation of 6/1-90 and aryliodide, an ee-value of only 12% was obtained. 

B(3,5-(CF3)2C6H3)4-.512 Palladium complexes with a hemilabile terdentate carbene ligand, 1,3-bis(pyl)imidazol-2-ylidene, were active toward the catalytic polymerization of CO/norbornylene.513 Palladium complexes of cz s-bidentate C4-bridged diphosphines cis- and trans- 1,2-bis [(diphenylphosphino)methyl]cyclohexane, e fl o,e fl o-2,3-bis[(diphenylphosphino)methyl] norbornane,... 

However, the practical, direct synthesis of functionalized linear polyolefins via coordination copolymerization olefins with polar monomers (CH2 = CHX) remains a challenging and industrially important goal. In the mid-1990s Brookhart et al. [25, 27] reported that cationic (a-diimine)palladium complexes with weakly coordinating anions catalyze the copolymerization of ethylene with alkylacrylates to afford hyperbranched copolymers with the acrylate functions located almost exclusively at the chain ends, via a chain-walking mechanism that has been meticulously studied and elucidated by Brookhart and his collaborators at DuPont [25, 27], Indeed, this seminal work demonstrated for the first time that the insertion of acrylate monomers into certain late transition metal alkyl species is a surprisingly facile process. It spawned almost a decade of intense research by several groups to understand and advance this new science and to attempt to exploit it commercially [30-33, 61]. 

Y. Kayaki, Y. Noguchi, S. Iwasa, T. Ikariya, R. Noyori, An Effitient Carbonylation of Aryl Halides Catalysed by Palladium Complexes with Phosphite Ligands in Supercritical Carbon Dioxide , Chem Commun. 1999, 1235-1236. 

Heck reactions have also been used by Helmchen et al. for a two-component domino process of a,co-amino-1,3-dienes.1721 By using palladium complexes with chiral phosphino-oxazolines as catalysts an enantiomeric excess of up to 80 % is achieved. In a... 

Table 3.3 Scavenging palladium complexes with SiliaBond Thiol.

Structural Identification of a Palladium Complex with a Chiral Sulfoxide Ligand... 

The mechanism of this reaction was considered on the basis of hydropalladation (Scheme 14). To minimize steric repulsions, the palladium hydride complex approaches the C=CH2 moiety of the allene in the anti-Markovnikov mode from the opposite side of the substituent. This addition gives a 7t—allyl palladium complex with the (Z)-configuration,18 which is converted to the (Z)-product by C-P bond formation, with regeneration of the Pd(0) catalyst. 

Slagt MQ, van Zwieten DAP, Moerkerk A, Gebbink R, van Koten G. NCN-pincer palladium complexes with multiple anchoring points for functional groups. Coord Chem Rev 2004 248 2275-2282. 

In 1998, Strukul and coworkers presented a diphosphine-palladium complex, with which the Baeyer-Villiger oxidation of cyclic and for the first time also acyclic ketones could be catalyzed in the presence of various peroxidic oxidants (H2O2, TBHP, KHSO5, carbamide peroxide) (Scheme 158)4 . pj-om these oxidants H2O2 turned out to be the most efficient one, whereas almost no conversion was obtained (<1% after several days) with TBHP. The authors could show that an increase in the bite angle of the diphosphine caused... 

Table 18.3 P- and Selected H-NMR Chemical Shifts1 of Palladium Complexes with Diphosphanes79 (5 CDC13.3 P at 32.4 or 36.4 MHz)...

Nickel(O) or palladium(II) compounds in stoichiometric amounts promote the ring enlargement of simple alkyl-substituted 1,2-divinylcyclobutanes in benzene at room temperature to give 1 1 metal complexes of cycloocta-1,5-dienes.119 Destruction of the palladium complexes with potassium cyanide affords the free cycloocta-1,5-dienes. The stereochemistry observed is the same as in the thermal reaction at 150°C. 

In the previous sections, double silylation was facilitated by using more reactive substrates such as alkynes and dienes with activated and strained disilanes. However, the use of palladium complexes with certain ligands allows successful reaction with the unactivated disilanes. 

The 1,4-disilylation of a,/3-unsaturated ketones has been reported by Ito and co-workers.172 Unsymmetrically substituted disilanes, PhCl2SiSiMe3 and Cl3SiSiMe3, undergo reaction in the presence of catalytic amounts of palladium complexes with tertiary alkyl phosphine or bidentate phosphine ligands to yield /3-silyl ketones [Eq. (64)]. 

Fig. 11. Square-planar platinum and palladium complexes with large y.

Polystyrene-bound secondary aliphatic amines and /V-alkyl amino acids can be ally-lated by treatment with a diene and an aryl iodide or bromide in the presence of palla-dium(II) acetate (Entry 14, Table 10.3). As the diene, 1,3-, 1,4-, and 1,5-dienes can be used, and, besides aryl halides, heteroaryl bromides have also been successfully used [63], This remarkable reaction is likely to proceed via the formation of an aryl palladium complex, with subsequent insertion of an alkene into the C-Pd bond. The resulting organopalladium compound does not undergo ( -elimination (as in the Heck reaction), but isomerizes to an allyl palladium complex, which reacts with the amine to give the observed allyl amines. 

In 1998, a new type of Pd(II) binuclear complex was reported which was effective for Mannich reactions of an imine derived from glyoxylate and anisidine with silicon enolates [38,39]. In these reactions, use of solvents including a small amount of water was essential. It was shown that water played an important role in this system water not only activated the Pd(II) complex to generate a cation complex, but also cleaved the N-Pd bond of the intermediate to regenerate the chiral catalyst. This reaction reportedly proceeded via an optically active palladium enolate on the basis of NMR and ESIMS analyses. A unique binuclear palladium-sandwiched enolate was obtained in the reaction of the p-hydroxo palladium complex with the silyl enol ether [(Eq. (9)]. 

---