Highly Efficient Degradation of Thiophosphate Pesticides Catalyzed by Cyclopalladated Ferrocenylketimines

In this paper, four functional substituted derivatives of cyclopalladated ferrocenyl- ketimines 1~4, which were as mimetics of metal-dependent esterases for catalyzing the hydrolysis of thiophosphoric acid esters pesticides, were synthesized and characterized. All the four cyclopalladated complexes can efficiently catalyze the degradation of thiophosphoric acid pesticides, such as methyl parathion. The Pd catalyst with coordinated oxime is more active and exhibits an increased selectivity towards sulfur containing pesticides.

Chiral palladium complexes based on derivatives of benzylamine and 2α-hydroxypinan-3-one

Synthesized and characterized new chiral palladium complexes, some of which contain asymmetric donor nitrogen atom. Nitrogen-containing derivatives (+) - and (-)-2α-hydroxypinan-3-one- (1R,2R,5R)-3-(benzylimino)-2,6,6-trimethylbicy- clo[3.1.1]heptane-2-ol (HL1), (1S,2S,3S,5S)-3- (benzylamino)-2,6, 6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL2), (1R,2R,5R)-3-((S)-α-methyl- benzylimino)-2,6,6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL3), (1R,2R,3R,5R)-3-((S)-α-methyl- benzylamino)-2,6,6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL4) -were studied as optically active ligands.

Enantiomeric Excess Determination of Amino Acids with Chiral Cyclopalladated Ferrocenylimine

An efficient NMR determination of the enantiomeric excess of the amino acids can be achieved using chloro-bridged dimer R- (+)-{Pd [(eta(5)-C5H5)Fe (eta(5)-C5H3CMe=NAr)] (mu-Cl)}2 (Ar=p-CH3C6H4) (R-1).

Suzuki Coupling Reaction Catalyzed by Cyclopalladated Complexes of Tertiary Arylamines in Ionic Liquid

Suzuki cross-coupling reaction of phenylboronic acid with aryl halides catalyzed by cyclopalladated complexes of tertiary arylamines immobilized in ionic liquid [Bmim]^＋BF4^- was reported. The catalytic system proved to be efficient and be reused at least 3 times without significant loss of activity.

Synthesis and Structures of New Cyclopalladated Ferrocenylimines

The new complexes, [PdCl{C5H4FeC5H4CHRN=CHC4H3O}（Ph3P）] （R= H, CH3） were synthesized via two novel Schiff bases （C5H5FeC5H4CHRN=CHC4H3O, R= H, CH3） with lithium tetrachloropalladate （Ⅱ）, and characterized by IR, elemental analysis, ^1H NMR. Complex 5a was further determined by X-ray single crystal diffraction. We found that it contained an intramolecular N→Pd coordination in the compound 5a, and the palladium atom was bound to the unsubstituted Cp ring. The Pd-N, Pd-C （I） and Pd-O bond lengths were 2.121 （3）, 2.008 （4） and 2.990 ）A, respectively.

Homocoupling of Aryl Iodides Catalyzed by Cyclopalladated Complexes of Tertiary Arylamines

Homocoupling of aryl iodides catalyzed by cyclopalladated complexes of tertiary arylamines gives symmetric biaryls with good yields in DMA or ionic liquid [Bmim]BF4. This catalytic alternative of the Ullmann reaction has proved to be sensitive to both electronic and steric factors of substrates.

Palladium-catalyzed late-stage mono-aroylation of the fully substituted pyrazoles via aromatic C-H bond activation

The palladium-catalyzed late-stage aroylation of 4-methyl-1,5-diaryl-lH-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp^2-H bond activation with broad substrate scope and good functional group tolerance. A dual-core dimeric palladacycle is confirmed by X-ray single crystal crystallography, and probably serves as an active species in the catalytic cycle.

Heck Reaction Catalyzed by Palladacycle in Neat Water

Cyclopalladated ferrocenylimine has been found to be a type of excellent phosphine-free catalyst for Heck reactions in neat water with both higher yields and turnover numbers than those reported in the literature up to now. Some commercial emulsifying agents, including the commonly used quaternary ammonium salts, have been proved to be excellent additives in the catalysis of the reactions. Not only aromatic iodide, but also aromatic bromide could be coupled with the olefins. All reactions were able to be conducted in air under refluxing condition.

Self-assembly Palladacycle Thiophene Imine Monolayer Investigating on Catalytic Activity and Mechanism for Coupling Reaction

An ordered cyclopallated thiophene imine self-assembly monolayer(Si@Pd3TI)was designed and fkbri-cated.It was characterized by water contact angle(WCA),ultraviolet-visible spectroscopy(UV),cyclic voltanmie-try(CV),infrared(IR)spectrum,atomic force microscopy(AFM)and X-ray photoelectron spectroscopy(XPS).Its catalytic performance for Suzuki coupling reaction and catalytic mechanism were systematic investigated.Si@Pd3TI was validated as a heterogeneous catalyst identified by poisoning tests,hot filtration test and three-phase test.The heterogeneous catalytic mechanism was investigated by WCA,UY Raman spectrum(RS),AFM,XPS and density functional theory(DFT).The catalytic mechanism proceeded via surface-catalysis process,on which the Pd(Ⅱ)/Pd(Ⅰ)/Pd(0)synergistic active center acted likely as"multimetallic cluster".It played a great role for cataly-zing coupling reaction,in which the real active species was Pd(Ⅰ).

Cyclopalladated Ferrocenylimine Catalyzed Chlorination of 2-Arylbenzoxazoles

An efficient and facile protocol for palladacycle-catalyzed chlorination of 2-arylbenzoxazoles was developed. The results represent the first examples involving the palladacycle as the catalyst for such chlorination. This chlori- nation was not a ligand-directed ortho-C--H activation, but an electrophilic substitution process at the para-position of the nitrogen atom in the benzo ring of benzoxazole moiety, the regiochemistry of which had been confirmed by HMBC spectral analysis. The catalytic system could tolerate various halogen atoms, such as F, Cl and Br, affording the corresponding products in moderate to excellent yields.

Crystal Structure of Chiral Acetato-bridged Binuclear Cyclopalladated Complex [Pd(μ-O_2CMe)(S-C_6H_4CHMeNH_2)]_2

Reaction of ( S) α methylbenzylamine with Pd(OAc) 2 in anhydrous HOAc produced the chiral complex [Pd( μ O 2CMe)( S C 6H 4CHMeNH 2)] 2 (1). The complex was characterized by 1H NMR spectroscopy, elemental analysis and a single crystal X ray analysis. The X ray crystal structure analysis revealed that complex 1 has four isomers: two outer and two inner isomers.

Heck Reaction of Iodoarenes with Methyl Acrylate Catalyzed by Cyclopalladated Complexes of Tertiary Arylamines Immobilized in Ionic Liquid [Bmim]^+BF_4^-

Heck reaction of iodoarenes with methyl acrylate, catalyzed by cyclopalladated complexes of tertiary arylamines, was investigated in ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ( +BF - 4). The products can be isolated conveniently from the ionic liquid-catalyst system. The catalysts could be reused for more than 10 times still with satisfactory catalytic activity.