吡啶/喹啉单亚胺镍(Ⅱ)配合物的合成及液体聚丁二烯的制备

金属配合物中引入侧臂软电子给体膦或硫是提高配合物催化性能的有效途径。本文合成了一系列吡啶/喹啉单亚胺NNP三齿Ni(Ⅱ)配合物(2a~2d),采用傅里叶变换红外光谱、元素分析及单晶衍射对配合物进行了表征。配合物2a为方形锥体构型,配合物2d为三角双锥构型。该系列配合物在倍半乙基氯化铝(EASC)活化下,催化合成了数均相对分子质量为4200~7700、顺-1,4结构的摩尔分数在74.5%~79.9%的液体聚丁二烯。催化活性随着聚合温度的升高而提高。在90℃时,催化体系仍有很高的聚合活性,聚丁二烯的收率达到85.9%,表明其具有高的热稳定性。     

Synthesis and Characterization of Metal Complexes of a New Unsymmetrical Tridentate NNS Schiff Base Ligand: X‐ray Crystal Structure Determination of Nickel(II) Complex

A new unsymmetrical tridentate NNS Schiff base ligand, 2‐(2‐nitrophenylthio)‐N‐((pyridine‐2‐yl)methylene)benzenamine (L), and its Mn(II ), Ni(II ), Cu(II ), and Zn(II ) complexes were synthesized. These compounds were characterized by different physicochemical and spectroscopic techniques. The molecular structure of [NiL₂ ](ClO₄ )₂ was determined by single‐crystal X‐ray diffraction. In this complex, two ligands coordinate through azomethine‐N, pyridine‐N, and thioether‐S, forming a mononuclear 6‐coordinate distorted octahedral geometry about a nickel.     

Ullmann CO coupling of sterically hindered secondary alcohols using excess amount of strongly coordinating monodentate ligands

A new effective copper catalyzed CO coupling reaction using excess amount of strongly coordinating monodentate ligands was successfully developed. Among the DMAP-type monodentate ligands, 4-pyrrolidinopyridine afforded the best results. The developed reaction is widely applicable for the synthesis of various hindered or acyclic secondary alkyl-aryl ethers. In this study, a novel and remarkable acceleration of the coupling reaction using excess amount of monodentate ligands was discovered.     

Palladium nanoparticles stabilized by phosphine ligand for aqueous phase room temperature suzuki-Miyaura coupling

Water soluble phosphine ligand triphenylphosphine-3,3′,3″-trisulfonic acid trisodium salt (TPPTS) was used as the stabilizer as well as the activator to the palladium nanoparticles, which showed a high catalytic performance for aqueous phase Suzuki-Miyaura coupling reaction at room temperature.     

The Cu-catalyzed asymmetric conjugate addition with chiral diphosphite ligands derived from D-(-)-tartaric acid

A series of diphosphite ligands, which were derived from D-(-)-tartaric acid, have been synthesized and successfully applied in the Cu-catalyzed asymmetric conjugate addition of organozincs to enones. There was a synergic effect between the stereogenic centers of the D-(-)-tartaric acid skeleton and the axially H₈-binaphthyl moieties of ligand 2c. And ligand 2c shows a comparative catalytic performance to ligand 1-N-benzylpyrrolidine-3,4-bis[(S)-1,1′-H₈-binaphthyl-2,2′-diyl]phosphite-L-tartaric acid1d derived from L-(+)-tartaric acid. Therefore, for cyclic enones, both enantiomers of the addition products can be obtained in high enantioselectivity (ees up to 96%) by simply selecting ligands 1d or 2c derived from D-(-)-tartaric acid or L-(+)-tartaric acid. Moreover, the sense of enantiodiscrimination of the products was mainly determined by the configuration of the binaphthyl phosphite moieties.     

Suzuki-Miyaura cross-coupling reaction of aryl chlorides with aryl boronic acids catalyzed by a palladium dichloride adduct of N-diphenylphosphanyl-2-aminopyridine

One palladium dichloride adduct of a phosphine-pyridine ligand N-diphenylphosphanyl-2-aminopyridine (L₁) [(L₁)PdCl₂] (1) has been prepared and structurally characterized. Compound 1 can be used as an effective catalyst for the Suzuki-Miyaura cross-coupling reactions of unreactive aryl chlorides with aryl boronic acids, and worked much better than its mono- or bidentate phosphine ligands. The reactions with a wide scope of substrates proceeded to give desired products in good to excellent yields.     

CuII-catalysed asymmetric 1,3-dipolar cycloaddition of azomethine ylides with a chiral ferrocene-derived P,N-ligand

A ferrocene-derived P,N-heterodonor ligand was effectively used in a Cu(OAc)₂·H₂O-catalysed asymmetric 1,3-dipolar cycloaddition of azomethine ylides with maleate derivatives, affording cycloadducts with high yields (up to 96%), diastereoselectivities (>99 dr), and enantioselectivities (up to 99% ee).     

Toxic metal complexes of macrocyclic cyclen molecule – synthesis,structure and complexing properties

Toxic metal (Cd²⁺, Hg²⁺, Pb²⁺, and Ag⁺) complexes with the tetradentate macrocyclic ligand - cyclen (1,4,7,10-tetraazacyclododecane, [12]aneN₄, L) were prepared and studied in the solid state by IR, X-ray diffraction, elemental and thermal analysis. Diffraction results have yielded three molecular structures, [Cd([12]ane-κ⁴N^1,4,7,10)(NO₃)₂)] (1), [Hg([12]ane-κ⁴N^1,4,7,10)(NO₃-κ²O,O`)]NO₃ (2), [Pb₂([12]ane-κ⁴N^1,4,7,10)₂][Pb(NO₃)₆] (3) and one polymeric structure {[Ag₂([12]ane-κ³N^1,4,7)(μ₂-[12]aneN¹⁰)](NO₃)₂?2H₂O)}_n (4) featuring a unique coordination mode not observed before with cyclen as a ligand. The monodentate (1) and chelate (with small bite angle 50.3(3)°, (2) coordination modes of nitrate ligands were confirmed. Stereochemically active 6s² lone pair was suggested in 3 and DFT results confirmed no significant metal–metal covalent bond. The stability constants of the complexes with Cd²⁺ and Pb²⁺ ions were determined by potentiometric methods in aqueous solutions. Additionally, the structures of complexes in solution were observed by ¹H NMR. Both methods confirm similar cyclen complexing properties toward Zn²⁺ biometal and Cd²⁺, Pb²⁺ toxic metals.     

Two new Keggin-type polyoxometalate-based organic-inorganic hybrid compounds with metal ions and chelate ligands

Two new hybrid compounds with chemical formulas [Co(L₁)₂(H₂O)₂]₂[SiW₁₂O₄₀]·6H₂O (1) and [Cu₂(C₉H₂₂ N)₂(L₂)₂][SiW₁₂O₄₀]·2H₂O (2) (L₁ = 3,3′-diamino-5,5′-bis(1H-1,2,4-triazole), L₂ = 1,2-bis(3-(2-pyridyl)pyrazole-1-ylmethyl)benzene, C₉H₂₂ N = tripropylamine) were prepared in a hydrothermal reaction system containing Keggin-type polyoxometalates (POMs), transition metal (TM) salts (cobalt salts and copper salts), and chelate L₁/L₂ ligands. X-ray structural analysis reveals that 1 and 2 possess 3-D supramolecular host frameworks with large cavities and the polyoxoanions SiW₁₂ reside in these cavities as the guest templates. The photocatalytic activities of 1 and 2 were investigated. Both compounds show efficient catalytic activity for degradation of RhB with 1 > 2. The loading amount of the POM units and the structural features of these POM-based organic-inorganic hybrid compounds may be necessary factors that affect the activity of catalysts in the photocatalytic degradation.     

Anion and pH-regulated assembly of three Cd(II) coordination polymers based on 3,5-di(1H-benzo[d]imidazol-1-yl)benzoate

Three coordination polymers, {[CdI(DBBA)]?0.5H₂O}_n (1, DBBA = 3,5-di(1Hbenzo[d]imidazol-1-yl)benzoate), [Cd(DBBA)(CH₃COO)]_n (2) and [Cd(DBBA)₂]_n (3), were obtained through reactions between Cd(II) salts and 3,5-di(1H-benzo[d]imidazol-1-yl)benzoic acid under different pH conditions. Compounds 1 and 2 are 3-D frameworks with rtl topology based on different binuclear Cd(II) secondary building units. Compound 3 was formed at lower pH and showed a 1-D chain assembled with M₂L₂ ring units. Moreover, phase purities, thermal behaviors, and photoluminescent properties have also been investigated.