Synthesis of a New Type of Amphilic and Water - soluble Tertiary Phosphine Ligands Substituted by an Ethoxylated Phosphonic Acid Chain and Their Palladium Complexes

The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N- (CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in good yield; the palladium (II) complexes of the ligands 3a~c with 2:1 or 4:1 -PPh2 to Pd2+ molar ratio were also prepared and characterized .

Synthetic and structural chemistry of nickel(Ⅱ) complexes containing dithiolato and phosphine ligands Ⅰ. Preparation and crystal structure of Ni_2(PPh_3)_2(edt)_2

A nickel(Ⅱ) complex containing both dithiolato and phosphine ligands, Ni_2(PPh_3)_2(edt)_2 (edt = SCH_2CH_2S^(2-)), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic system, space group P-1, with a = 10.693(3), b = 17.457 (6), c = 10.606 (3)A, α= 102.84(2), β = 96.49 (2), γ = 82.56(3)°; V = 1906.8 A^3; D_c = 1.439g.cm^(-3) for Z=2; the final con- ventional R was 0.052 based on 3338 observed reflections. Nickel atoms are linked by two sulfur atoms from two edt ligands with the Ni--Ni distance of 2.893 A, and each Ni atom is coordinated by one phosphorus atom and three sulfur atoms with a square-planar geometry, where the average: length of Ni--S bond is 2.180 A and Ni--P bond 2.188 A. The UV-Vis and ~1H NMR spectra have also been recorded.

Alkoxy substituted MeO-BIPHEP-type diphosphines ligands for asymmetric hydrogenation of aryl ketones

In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.

A novel thermoregulated phosphine ligand used for the Rh-catalyzed hydroformylation of mixed C_(11-12) olefins in aqueous/organic biphasic system

A novel thermoregulated phosphine ligand PhP(CHCHO)CH(n=22) was synthesized and used for the Rh-catalyzed hydroformylation of mixed Colefins in aqueous/organic biphasic system.Under the optimized conditions,pressure =5 MPa (H:CO=1:1),phosphine/Rh =13(molar ratio),reaction time =6 h and temperature =130℃,the conversion of Colefins and the yield of aldehyde are 99%and 94%,respectively.The catalyst retained in aqueous phase can be easily separated from the product-containing organic phase by simple phase separation and the catalytic activity remains almost constant after four consecutive cycles.

Ionic palladium complex as an efficient and recyclable catalyst for the carbonylative Sonogashira reaction

The neutral palladium（Ⅱ） complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-imidazolyl]dichloropalladium（Ⅱ）（1A） ligated by thiazolylimidazolyl-based phosphine（L1） in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-3-methylimidazolium]dichloropalladium（Ⅱ） trifluoromethanesulfonate（2A） ligated by thiazolylimidazolium-based phosphine（L2） after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.

Studies on the Recycling Efficiency of Thermoregulated Phase-separable Rh/PETPP Complex Catalyst

Effects on the recycling efficiency of thermoregulated phase-separable Rh/PETPP (P-[p-C6H4O(CH2CH2O)nH]3, N=3n) complex catalyst involved in hydroformylation of 1-decene are for the first time presented. It was found that the loss of Rh is dependent greatly on the composition of phosphine ligand PETPP and the organic solvent employed in the reaction.

Synthesis,Structure and Electrochemistry of Triruthenium Cluster Complex [Ru_3(μ_3- O)(μ-CH_3CO_2)_6(py)_2(PPh_2py)](PF_6)·CH_2Cl_2

The reaction between [Ru3(3-O)(-CH3CO2)6(py)2(MeOH)](PF6) (py = pyri- dine) and diphenyl-2-pyridyl-phosphine (PPh2py) gave the triruthenium cluster complex [RuIII3(3-O)(-CH3CO2)6(py)2(PPh2py)](PF6)CH2Cl2 (C40H44Cl2F6N34O13P2Ru3) which was characterized by elemental analysis, IR, UV-Vis and 31P NMR spectroscopy, and X-ray single- crystal diffraction. The structure is of monoclinic, space group P21/n with a = 16.3896(1), b = 16.8773(2), c = 19.1438(2) ? b = 95.888(1), V = 5267.47(9) ?, Mr = 1324.83, Dc = 1.671 g/cm3, F(000) = 2636, m = 1.092 mm-1 and Z = 4. The final refinement gave R = 0.0508 and wR = 0.1111 for 6987 observed reflections (I > 2s(I)). Three Ru(III) atoms bridged by m3-oxo donor form an approximately isosceles triangle. The complex shows three quasireversible one- electron processes at E1/2 = 1.22 +0.03 and 1.20 V vs. Ag/AgCl.

Enhancement on Hemilabile Phosphine-Amide Palladium and Nickel Catalysts for Ethylene(Co)Polymerization with Polar Monomers Using a Cyclizing Strategy

To address the issue of hemilabile catalyst in olefin polymerization catalysis, a cyclizing strategy was used to construct novel N-bridged phosphine-carbonyl palladium and nickel catalysts, resulting in improvements on ethylene(co)polymerizations. The N-bridged phosphinecarbonyl Pd catalysts(Pd1-Pd5) and Ni catalysts(Ni1-Ni5) bearing five-to eight-membered-ring structures were designed and synthesized.Catalytic performance for ethylene(co)polymerization became better as the size of N-containing bridge increased. The seven-membered-ring bridged catalysts Pd4 and Ni4 exhibited the best performance in terms of catalytic activity, polymer molecular weight and incorporation of acrylates and acrylic acid. The better performance of these catalysts bearing larger-size bridges was tentatively attributed to the methyleneinduced higher electron density around nitrogen, which strenghtens the coordination of carbonyl group to metal center, and also to the steric effect offered by this cyclization. This work provides a new strategy to enhance hemilabile polymerization catalysts.

Influence of bidentate structure of an aryl phosphine oxide ligand on photophysical properties of its Eu~Ⅲ complex

The bidentate phosphine oxide ligand 1,8-bis(diphenylphosphino) naphthalene oxide (NAPO) and its EuⅢ complex 1 Eu(TTA)3(NAPO) (TTA=2-thenoyltrifluoroacetonate) were chosen to study the effect of bidentate phosphine oxide ligand on the photophysical properties of the corresponding complex. The intramolecular energy transfer processes of 1 were studied. The investigation showed that with bidentate structure NAPO could suppress solvent-induced quenching by enforcing the ligand-ligand interaction and the rigidi...

Monodentate phosphorus-coordinated palladium(Ⅱ)complexes as new catalyst for Mizoroki-Heck reaction of aryl halides with electron-deficient olefins

Four novel palladium（（Ⅱ）） complexes coordinated by phosphorus atoms from both 3,5-disubstituted-1H- 1,2,4-diazaphospholes in monodentate fashion were developed as efficient catalyst for the Mizoroki- Heck reaction of aryl halides with electron-deficient olefins. The coupling reaction of awl halide bearig different functional groups with olefin derivatives took place and the corresponding products were isolated in good to excellent yields under optimal conditions. The procedure exhibits good functional group tolerance and wide substrate scope. This Mizoroki-Heck reaction was further achieved using Pd（OAc）2 and 3,5-di-isopropyl-1H-1,2,4-diazaphospholes as combined catalyst, which provide the convenient and alternative method in organic synthesis

Dinitrogen Functionalization Affording Structurally Well-Defined Cobalt Diazenido Complexes

Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functionalization by treating the complex 3b with i Pr_(3)SiCl afforded the first structurally characterized cobalt diazenido complex 5.These complexes 3–5 were found to be effective catalysts for the transformation of N2 into N(SiMe_(3))_(3).The electronic structure of the cobalt diazenido complex 5 is supported by quantum computational calculations based on stateof-the-art energy decomposition analysis(EDA)in conjunction with the natural orbitals for chemical valence(NOCV)method.

Propylene Dimerization by (η~5-C_9H_7)_2 Nickel(II) Catalytic System

The catalytic performance of Ni( η 5 Ind) 2 complex in the dimerization of propylene was studied in combination with an organoaluminum co catalyst, eventually in the presence of a phosphine ligand. The effects of the type of aluminum co catalyst and its relative amount, the nature of phosphine ligand and P/Ni ratio as well as the reaction temperature were examined. The results indicated that the nickel precatalyst exhibited high productivity for the propylene dimerization together with organoaluminum. It was likely to strongly modify the reactivity in the catalytic system when using phosphine ligand as additives, especially at the reaction temperature below 0 ℃. The catalytic system based on Ni( η 5 Ind) 2 complex displayed an extremely high productivity (TOF up to 169000 h -1 ) and a good regioselectivity to 2,3 dimethylbutenes (2,3 DMB) in dimers (66 4%) under proper reaction parameters.