The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-1,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling react...The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-1,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling reaction of terminal alkynes with different acyl chlorides in the presence of triethylamine as base,giving excellent ynones under aerobic conditions.展开更多
A new Pd-PEPPSI complex(2) with the bromo groups on the para-positions of N-aryl moieties of NHC has been synthesized and characterized by NMR and X-ray single-crystal diffraction. Complex 2 crystallizes in monoclinic...A new Pd-PEPPSI complex(2) with the bromo groups on the para-positions of N-aryl moieties of NHC has been synthesized and characterized by NMR and X-ray single-crystal diffraction. Complex 2 crystallizes in monoclinic, space group P2_1/c with a = 11.8790(8), b = 14.3038(10), c = 15.9905(11) ?, β = 101.291(2)°, V = 2664.4(3) ?3, Z = 4, D_c = 1.722 Mg/m^3, μ = 3.913 mm^(-1), F(000) = 1352, the final R = 0.0682 and wR = 0.1914 for 15113 observed reflections(I > 2σ(I)), R(all data) = 0.0970, w R(all data) = 0.2115, completeness to theta of 25.00 is 100.0% and GOOF = 1.035. Influenced by the electron-withdrawing bromo groups, the Pd-PEPPSI complex(2) showed high catalytic activity for the Suzuki-Miyaura cross-coupling reactions of aryl chlorides and arylboronic acids with a low catalyst loading(0.05 mol%) at room temperature in air.展开更多
A novel crystal with the molecular formula [Pd（DCA）（bipy）]2 [Pd（bipy）Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate （Na2 （DCA）,DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate） an...A novel crystal with the molecular formula [Pd（DCA）（bipy）]2 [Pd（bipy）Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate （Na2 （DCA）,DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate） and 2,2-bipyidine （bipy） through the hydrothermal method.The complex was characterized by elemental analysis and infrared spectroscopy.The structure of the complex was determined by single-crystal X-ray diffraction,which is of triclinic system,space group P1 with a=13.6818（7）,b=14.8426（8）,c=15.0043（8）,α=97.319（3）,β=92.521（3）,γ=105.776（2）°,V=2898.4（3） 3,Dc=1.545 g·cm-3,Z=1,F（000）=1420,S=0.852,the final R=0.0525 and wR=0.1777 for 13634 observer reflections （I〉2σ（I））.The binding reaction of the complex with ct-DNA and bovine serum albumin （BSA） was studied by fluorescence spectroscopy.The results indicated that the complex binds to ct-DNA via the partial intercalation.The binding constant K A of the complex interaction with BSA was 3.98×10 5 L·mol-1 and one binding site would be formed.The antiproliferative activity of the complex against human hepatoma cells （SMMC7721） in vitro is much higher than that of Na 2 （DCA）.展开更多
To develop a luminescent material with high color purity, luminous efficiency, and stability, we synthesized diketone by carbonylative Suzuki coupling in the presence of Pd(NHC) complex as the catalyst. Carbonylative ...To develop a luminescent material with high color purity, luminous efficiency, and stability, we synthesized diketone by carbonylative Suzuki coupling in the presence of Pd(NHC) complex as the catalyst. Carbonylative coupling of 4,4’-diiodobiphenyl and phenylboronic acid was investigated to study in detail the catalytic ability of the Pd(NHC) complex. Reactions were carried out using both CO and metal carbonyls. Bis-(1,3-dihydro-1,3-dimethyl-2H-imidazol- 2-ylidene) diiodo palladium was used as the catalytic complex. Reaction products biphenyl-4,4’-diylbis (phenyl- methanone) 3 and (4’-iodobiphenyl-4-yl)(phenyl) methanone 4 were obtained as a result of CO insertion into the palladium(II)-aryl bond. However, when pyridine-4-yl boronic acid was used in place of phenylboronic acid as the starting reagent, synthetic reaction yielding 3 and 4 were found not to occur.展开更多
The reactions of 18-crown-6with Na 2M(SCN)4(M=Pd,Pt )were studied and the complexNa (18-C-62 (H2O) nPd(SCN)4 n and complex2Na (18-C-6) 2 (H 2 O nPt (SCN) 4 n were characterized by ele-mental analysis,IR and X-ray diff...The reactions of 18-crown-6with Na 2M(SCN)4(M=Pd,Pt )were studied and the complexNa (18-C-62 (H2O) nPd(SCN)4 n and complex2Na (18-C-6) 2 (H 2 O nPt (SCN) 4 n were characterized by ele-mental analysis,IR and X-ray diffra ction analysis.The complexes belon g to monoclinic,space group P2 1 /n with cell dimensions,1:a=1.05734(7),b=1.42250(10),c=1.47762(10)nm,β=107.5330(10)°,V=2.1192(2)nm 3 ,Z =2,D calcd =1.460g·cm -3 ,F(000)=964,R 1 =0.0406,w R 2 =0.1264and2:a=1.05985(19),b=1.4237(3),c=1.4744(3)nm,β=107.096(3)°,V=2.1264(7)nm 3 ,Z =2,D calcd =1.690g·cm -3 ,F(000)=1028,R 1 =0.0292,w R 2 =0.0859.In the solid state,the comp lexes1and2show an one-dimensnal chain ofNa (18-C-6)狚 2 (H 2O)2+ complex cations andM(SCN) 4 2- (M=Pd,Pt )complex anions bridged by Na-N in-teractions.展开更多
基金the Research Council of Shahrood University of Technology for the support of this work
文摘The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-1,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling reaction of terminal alkynes with different acyl chlorides in the presence of triethylamine as base,giving excellent ynones under aerobic conditions.
基金Supported by the Natural Science Foundation of Tianjin(No.16JCYBJC19700)the National Natural Science Foundation of China(No.21771138)the Foundation of Development Program of Future Expert in Tianjin Normal University(No.WLQR201704)
文摘A new Pd-PEPPSI complex(2) with the bromo groups on the para-positions of N-aryl moieties of NHC has been synthesized and characterized by NMR and X-ray single-crystal diffraction. Complex 2 crystallizes in monoclinic, space group P2_1/c with a = 11.8790(8), b = 14.3038(10), c = 15.9905(11) ?, β = 101.291(2)°, V = 2664.4(3) ?3, Z = 4, D_c = 1.722 Mg/m^3, μ = 3.913 mm^(-1), F(000) = 1352, the final R = 0.0682 and wR = 0.1914 for 15113 observed reflections(I > 2σ(I)), R(all data) = 0.0970, w R(all data) = 0.2115, completeness to theta of 25.00 is 100.0% and GOOF = 1.035. Influenced by the electron-withdrawing bromo groups, the Pd-PEPPSI complex(2) showed high catalytic activity for the Suzuki-Miyaura cross-coupling reactions of aryl chlorides and arylboronic acids with a low catalyst loading(0.05 mol%) at room temperature in air.
基金Supported by the Natural Science Foundation of Zhejiang Province (Y407301)
文摘A novel crystal with the molecular formula [Pd（DCA）（bipy）]2 [Pd（bipy）Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate （Na2 （DCA）,DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate） and 2,2-bipyidine （bipy） through the hydrothermal method.The complex was characterized by elemental analysis and infrared spectroscopy.The structure of the complex was determined by single-crystal X-ray diffraction,which is of triclinic system,space group P1 with a=13.6818（7）,b=14.8426（8）,c=15.0043（8）,α=97.319（3）,β=92.521（3）,γ=105.776（2）°,V=2898.4（3） 3,Dc=1.545 g·cm-3,Z=1,F（000）=1420,S=0.852,the final R=0.0525 and wR=0.1777 for 13634 observer reflections （I〉2σ（I））.The binding reaction of the complex with ct-DNA and bovine serum albumin （BSA） was studied by fluorescence spectroscopy.The results indicated that the complex binds to ct-DNA via the partial intercalation.The binding constant K A of the complex interaction with BSA was 3.98×10 5 L·mol-1 and one binding site would be formed.The antiproliferative activity of the complex against human hepatoma cells （SMMC7721） in vitro is much higher than that of Na 2 （DCA）.
文摘To develop a luminescent material with high color purity, luminous efficiency, and stability, we synthesized diketone by carbonylative Suzuki coupling in the presence of Pd(NHC) complex as the catalyst. Carbonylative coupling of 4,4’-diiodobiphenyl and phenylboronic acid was investigated to study in detail the catalytic ability of the Pd(NHC) complex. Reactions were carried out using both CO and metal carbonyls. Bis-(1,3-dihydro-1,3-dimethyl-2H-imidazol- 2-ylidene) diiodo palladium was used as the catalytic complex. Reaction products biphenyl-4,4’-diylbis (phenyl- methanone) 3 and (4’-iodobiphenyl-4-yl)(phenyl) methanone 4 were obtained as a result of CO insertion into the palladium(II)-aryl bond. However, when pyridine-4-yl boronic acid was used in place of phenylboronic acid as the starting reagent, synthetic reaction yielding 3 and 4 were found not to occur.
文摘The reactions of 18-crown-6with Na 2M(SCN)4(M=Pd,Pt )were studied and the complexNa (18-C-62 (H2O) nPd(SCN)4 n and complex2Na (18-C-6) 2 (H 2 O nPt (SCN) 4 n were characterized by ele-mental analysis,IR and X-ray diffra ction analysis.The complexes belon g to monoclinic,space group P2 1 /n with cell dimensions,1:a=1.05734(7),b=1.42250(10),c=1.47762(10)nm,β=107.5330(10)°,V=2.1192(2)nm 3 ,Z =2,D calcd =1.460g·cm -3 ,F(000)=964,R 1 =0.0406,w R 2 =0.1264and2:a=1.05985(19),b=1.4237(3),c=1.4744(3)nm,β=107.096(3)°,V=2.1264(7)nm 3 ,Z =2,D calcd =1.690g·cm -3 ,F(000)=1028,R 1 =0.0292,w R 2 =0.0859.In the solid state,the comp lexes1and2show an one-dimensnal chain ofNa (18-C-6)狚 2 (H 2O)2+ complex cations andM(SCN) 4 2- (M=Pd,Pt )complex anions bridged by Na-N in-teractions.
