At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and pyridine N-oxide (triphenylphosphine oxide or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin) which affords t...At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and pyridine N-oxide (triphenylphosphine oxide or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin) which affords the last products as binuclear copper(II) complexes, [Cu(C5H5NO)-(C6H5COO)2]2(1), [Cu(OPPh3)(C6H5COO)2]2(2) and [Cu(C6H5COO)(C26H2oN2)](3, C26H2oN2 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin). The structure of the complexes were characterized by elemental analyses, IR spectra, TG-DTA and magnetic property. Crystals(1) are triclinic, space group P1,a=0.92617(36),b=1.06973(17), c=1.08813(29) nm, a=59.60(2)°, β=74.83(3)°,γ=72.80(2)°, V=0.880 nm3, Dc=1.520 g/cm3, Z=1, R=0.044, Rw=0.048, Mr=805.78, 3477 reflections with I > 3σ(I). Each copper(Ⅱ) ion is coordinated by two bridging bidentate benzoate ligands and one pyridine N-oxide or triphenylphosphine oxide to form dimeric binuclear molecules. The structure of the compound(1) shows a clear centre of symmetry.展开更多
Dibenzoyl peroxide undergoes oxidative addition with metallic copper powder and 2, 2’-bipyridine in a mixed solvent （methanol and tetrahydrofuran ） to afford copper（Ⅱ） complex [Cu（2, 2’-bipy） （C<sub>6&...Dibenzoyl peroxide undergoes oxidative addition with metallic copper powder and 2, 2’-bipyridine in a mixed solvent （methanol and tetrahydrofuran ） to afford copper（Ⅱ） complex [Cu（2, 2’-bipy） （C<sub>6</sub>H<sub>5</sub>COO）<sub>2</sub>]· H<sub>2</sub>O. The structure of the cornplex was solved by direct methods and refined by block-diagonal and full-ma-trix least-squares method to a final R of 0. 055 for 2654 independent reflections of I 】3σ（I）. Crystals are monoclinic,space group P2<sub>1</sub>/c , Mr= 479. 78 with cell parameters a= 6. 986（7） , b= 18. 833（1）, c= 17. 021（3）, β=97. 96（1）°, Z=4, Dc=1. 437g. cm￣（-3）, V= 2218. 1. Each copper ion is coordinated by the oxygen atoms of two benzoato groups and the nitrogen atoms of 2. 2’-bipyridine in a planar square geometry.展开更多
Two-electron reduction of[N_(2)NBn]Ti^(Ⅳ)Cl2(3)gave a highly reactive[N_(2)N]Ti^(Ⅱ)species,which underwent C—O bond activation of THF(tetrahydrofuran)to generate[N2NBn]Ti^(Ⅳ)[O(CH2)4](4)through oxidative addition....Two-electron reduction of[N_(2)NBn]Ti^(Ⅳ)Cl2(3)gave a highly reactive[N_(2)N]Ti^(Ⅱ)species,which underwent C—O bond activation of THF(tetrahydrofuran)to generate[N2NBn]Ti^(Ⅳ)[O(CH2)4](4)through oxidative addition.The resulted Ti^(Ⅳ)-Csp^(3)bond in oxametallacyclo-hexane was tantamount to the elaborately-designed Ti-alkyl complexes,competent to activate intramolecular Csp^(2)-H bond,forming ortho-cyclometalated complex[N_(2)NCH_(2)C_(6)H_(4)]Ti^(Ⅳ)(O^(n)Bu)(5).Key intermediates were isolated and fully characterized by X-ray crystal-lography.Mechanistic studies revealed that the oxidative addition of C-O bond took place at Ti^(Ⅱ)-center via a radical intermediate,while a Csp^(2)-H bond activation proceeded byσ-bond metathesis with a kitelike four-centered Ti^(Ⅳ)-transition state.展开更多
Main observation and conclusion A facile synthetic method for the construction of 3-azabicyclo[3.1.0]hexane in the presence of copper catalyst system was developed.The reaction proceeds through Michael addition of all...Main observation and conclusion A facile synthetic method for the construction of 3-azabicyclo[3.1.0]hexane in the presence of copper catalyst system was developed.The reaction proceeds through Michael addition of allylamines with allenes followed by copper-mediated intramolecular oxidative carbanion 5-exo-trig radical cyclization,affording potential biologically active 3-azabicyclo[3.1.O]hexane derivatives in moderate to high yields(42%-85%).展开更多
Reaction of Cu with dibenzovi peroxide, 2-aminothiazol gave a binuclear complex [Cu_2 (C_6H_5COO)_4(C_3H_4N_2S)_2]. Crystal of the title compound is monoclinic system space group P2_1/n , M_r = 807. 84 with cell param...Reaction of Cu with dibenzovi peroxide, 2-aminothiazol gave a binuclear complex [Cu_2 (C_6H_5COO)_4(C_3H_4N_2S)_2]. Crystal of the title compound is monoclinic system space group P2_1/n , M_r = 807. 84 with cell parameters a= 10. 685 ( 1 ), b=19. 028(6), c=17. 046(9) , β=96. 49(33)￣°, Z=4, V=3443. 4, D_c=1. 565 g/cm￣-3, μ= 14. 078 cm￣-1, F(000)= 824. The final refinement with 3429 observed reflections is converged with R= 0. 046 and R_w=0. 053. X-ray crystal structure analysis revealed that each copper ion is coordinated by four bridging birfentate benzoate ligandsand one Zaminothiazol to form a binuclear molecule. In the crvstal, there are intramolecular hydrogen bonds N (1)- H ( 1 )-O(4) and N (3)- H (3)-O(1) with NO distance of 3. 005, N-H-O angle of 131. 9°.展开更多
At room temperature, the reaction of dibenzoyl peroxide with metallic copper powder in the presence of pyridine affords the copper(Ⅱ) complex [Cu(C 5H 5N) 2(H 2O)\|(C 6H 5COO) 2]. Crystal is monoclinic, M r =483.002,...At room temperature, the reaction of dibenzoyl peroxide with metallic copper powder in the presence of pyridine affords the copper(Ⅱ) complex [Cu(C 5H 5N) 2(H 2O)\|(C 6H 5COO) 2]. Crystal is monoclinic, M r =483.002, space group Cc with parameters: a=6\^078(4), b=15.879(4), c=23.091(3), β=97.61(2)°, V=2209.1(2) 3, Z=4, D c =1\^464g/cm 3, μ =10.279 cm -1 , F(000)=996, R=0\^031, R w =0.036, 1595 reflections with I≥3σ(I ) were considered to be observed. Each copper(Ⅱ) ion is coordinated by two monodentate benzoate ligands, two pyridines and one water molecule. The complex is also characterized by its IR, XPS and thermal properties.展开更多
The process and mechanism of the ligand volume controlled Pd（PR3）2 （PR3=PH3, PMe3, and PtBu3） oxidative addition with aryl bromide were investigated, using density functional theory method with the conductor-like ...The process and mechanism of the ligand volume controlled Pd（PR3）2 （PR3=PH3, PMe3, and PtBu3） oxidative addition with aryl bromide were investigated, using density functional theory method with the conductor-like screening model. Association pathway and dissocia-tion pathway were investigated by the comparison of several energies. The cleavage energy of Pd（PR3）2 complex was calculated, as well as the oxidative addition reaction barrier energy of Pd（PR3）n （n=1,2） with aryl bromide in N,N-dimethylformamide solvent. This study proved that the ligands volume possessed a great impact on the mechanism of oxidative addition： less bulky ligand palladium associated with aryl bromide via two donor ligands,but larger bulky ligand palladium coordinated via monoligand.展开更多
Dibenzoyl peroxide undergoes oxidative addition on metallic copper powder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol and tetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'...Dibenzoyl peroxide undergoes oxidative addition on metallic copper powder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol and tetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'-bipy)]H_2O(1) and[Cu(C_6H_5COO)_2(C_3H_4N_2)_2](2).The structure was solved by direct methods and Fourier synthesis.C_(24)H_(20)N_2O_5Cu (1),Mr=479.78,space group P2(1)/c,a=6.986(7), b=18.833(I),c=17.021(3),α=γ=90°,Z=4,V=2218.1~3,Dc=1.443g/cm\+3,R=0.055 Rw=0.062.Complex(2),C_(20)H_(18)N_4O_4Cu(2),Mr=441.74,space group P2(1)/n,a=8.699(4), b=9.840(6),c=12.399(5),α=γ=90°,β=100.8°,Z=4,V=1010.9~3,Dc=1.654g/cm\+3,R=0.055, Rw=0.062.展开更多
基金Project supported by the National Natural Science Foundation of China and Nanjing Coordination Key Lab Foundation of China.
文摘At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and pyridine N-oxide (triphenylphosphine oxide or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin) which affords the last products as binuclear copper(II) complexes, [Cu(C5H5NO)-(C6H5COO)2]2(1), [Cu(OPPh3)(C6H5COO)2]2(2) and [Cu(C6H5COO)(C26H2oN2)](3, C26H2oN2 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin). The structure of the complexes were characterized by elemental analyses, IR spectra, TG-DTA and magnetic property. Crystals(1) are triclinic, space group P1,a=0.92617(36),b=1.06973(17), c=1.08813(29) nm, a=59.60(2)°, β=74.83(3)°,γ=72.80(2)°, V=0.880 nm3, Dc=1.520 g/cm3, Z=1, R=0.044, Rw=0.048, Mr=805.78, 3477 reflections with I > 3σ(I). Each copper(Ⅱ) ion is coordinated by two bridging bidentate benzoate ligands and one pyridine N-oxide or triphenylphosphine oxide to form dimeric binuclear molecules. The structure of the compound(1) shows a clear centre of symmetry.
文摘Dibenzoyl peroxide undergoes oxidative addition with metallic copper powder and 2, 2’-bipyridine in a mixed solvent （methanol and tetrahydrofuran ） to afford copper（Ⅱ） complex [Cu（2, 2’-bipy） （C<sub>6</sub>H<sub>5</sub>COO）<sub>2</sub>]· H<sub>2</sub>O. The structure of the cornplex was solved by direct methods and refined by block-diagonal and full-ma-trix least-squares method to a final R of 0. 055 for 2654 independent reflections of I 】3σ（I）. Crystals are monoclinic,space group P2<sub>1</sub>/c , Mr= 479. 78 with cell parameters a= 6. 986（7） , b= 18. 833（1）, c= 17. 021（3）, β=97. 96（1）°, Z=4, Dc=1. 437g. cm￣（-3）, V= 2218. 1. Each copper ion is coordinated by the oxygen atoms of two benzoato groups and the nitrogen atoms of 2. 2’-bipyridine in a planar square geometry.
基金support from the National Natural Science Foundation of China(Nos.21988101,21881220232,21811530004,21761132027,22071029,22201044,U19B6002)Key-Area Research and Development Program of Guangdong Province(2020B010188001).
文摘Two-electron reduction of[N_(2)NBn]Ti^(Ⅳ)Cl2(3)gave a highly reactive[N_(2)N]Ti^(Ⅱ)species,which underwent C—O bond activation of THF(tetrahydrofuran)to generate[N2NBn]Ti^(Ⅳ)[O(CH2)4](4)through oxidative addition.The resulted Ti^(Ⅳ)-Csp^(3)bond in oxametallacyclo-hexane was tantamount to the elaborately-designed Ti-alkyl complexes,competent to activate intramolecular Csp^(2)-H bond,forming ortho-cyclometalated complex[N_(2)NCH_(2)C_(6)H_(4)]Ti^(Ⅳ)(O^(n)Bu)(5).Key intermediates were isolated and fully characterized by X-ray crystal-lography.Mechanistic studies revealed that the oxidative addition of C-O bond took place at Ti^(Ⅱ)-center via a radical intermediate,while a Csp^(2)-H bond activation proceeded byσ-bond metathesis with a kitelike four-centered Ti^(Ⅳ)-transition state.
基金the Shanghai Comittee of Science and Technology(No.17ZR1407600)。
文摘Main observation and conclusion A facile synthetic method for the construction of 3-azabicyclo[3.1.0]hexane in the presence of copper catalyst system was developed.The reaction proceeds through Michael addition of allylamines with allenes followed by copper-mediated intramolecular oxidative carbanion 5-exo-trig radical cyclization,affording potential biologically active 3-azabicyclo[3.1.O]hexane derivatives in moderate to high yields(42%-85%).
文摘Reaction of Cu with dibenzovi peroxide, 2-aminothiazol gave a binuclear complex [Cu_2 (C_6H_5COO)_4(C_3H_4N_2S)_2]. Crystal of the title compound is monoclinic system space group P2_1/n , M_r = 807. 84 with cell parameters a= 10. 685 ( 1 ), b=19. 028(6), c=17. 046(9) , β=96. 49(33)￣°, Z=4, V=3443. 4, D_c=1. 565 g/cm￣-3, μ= 14. 078 cm￣-1, F(000)= 824. The final refinement with 3429 observed reflections is converged with R= 0. 046 and R_w=0. 053. X-ray crystal structure analysis revealed that each copper ion is coordinated by four bridging birfentate benzoate ligandsand one Zaminothiazol to form a binuclear molecule. In the crvstal, there are intramolecular hydrogen bonds N (1)- H ( 1 )-O(4) and N (3)- H (3)-O(1) with NO distance of 3. 005, N-H-O angle of 131. 9°.
文摘At room temperature, the reaction of dibenzoyl peroxide with metallic copper powder in the presence of pyridine affords the copper(Ⅱ) complex [Cu(C 5H 5N) 2(H 2O)\|(C 6H 5COO) 2]. Crystal is monoclinic, M r =483.002, space group Cc with parameters: a=6\^078(4), b=15.879(4), c=23.091(3), β=97.61(2)°, V=2209.1(2) 3, Z=4, D c =1\^464g/cm 3, μ =10.279 cm -1 , F(000)=996, R=0\^031, R w =0.036, 1595 reflections with I≥3σ(I ) were considered to be observed. Each copper(Ⅱ) ion is coordinated by two monodentate benzoate ligands, two pyridines and one water molecule. The complex is also characterized by its IR, XPS and thermal properties.
基金This work was supported by the National Natural Science Foundation of China （No.20776089） and the New Century Excellent Talents Program of Ministry of Education （No.NCET-05-0783）. The State Key Laboratory of Polymer Materials Engineering in Sichuan University was acknowledged for providing dmol3 modules and Prof. Ying Xue, Xiang-yuan Li, and Quan Zhu were grateful for the useful discussions.
文摘The process and mechanism of the ligand volume controlled Pd（PR3）2 （PR3=PH3, PMe3, and PtBu3） oxidative addition with aryl bromide were investigated, using density functional theory method with the conductor-like screening model. Association pathway and dissocia-tion pathway were investigated by the comparison of several energies. The cleavage energy of Pd（PR3）2 complex was calculated, as well as the oxidative addition reaction barrier energy of Pd（PR3）n （n=1,2） with aryl bromide in N,N-dimethylformamide solvent. This study proved that the ligands volume possessed a great impact on the mechanism of oxidative addition： less bulky ligand palladium associated with aryl bromide via two donor ligands,but larger bulky ligand palladium coordinated via monoligand.
文摘Dibenzoyl peroxide undergoes oxidative addition on metallic copper powder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol and tetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'-bipy)]H_2O(1) and[Cu(C_6H_5COO)_2(C_3H_4N_2)_2](2).The structure was solved by direct methods and Fourier synthesis.C_(24)H_(20)N_2O_5Cu (1),Mr=479.78,space group P2(1)/c,a=6.986(7), b=18.833(I),c=17.021(3),α=γ=90°,Z=4,V=2218.1~3,Dc=1.443g/cm\+3,R=0.055 Rw=0.062.Complex(2),C_(20)H_(18)N_4O_4Cu(2),Mr=441.74,space group P2(1)/n,a=8.699(4), b=9.840(6),c=12.399(5),α=γ=90°,β=100.8°,Z=4,V=1010.9~3,Dc=1.654g/cm\+3,R=0.055, Rw=0.062.
