The oxygenation constants （Ko2） of cobalt（Ⅱ） hydroxamates （CoL^1 2-CoL^3 2） with benzo-15-crown-5 （B15C5） pendants were measured over the range of -5 to ＋20 ℃, and the values of thermodynamic parameters （...The oxygenation constants （Ko2） of cobalt（Ⅱ） hydroxamates （CoL^1 2-CoL^3 2） with benzo-15-crown-5 （B15C5） pendants were measured over the range of -5 to ＋20 ℃, and the values of thermodynamic parameters （ΔH^0 and ΔS^0） were calculated based on these （Ko2） values, Meanwhile, these crowned complexes were employed to the oxidation for p-xylene to p-toluic acid with air at 110Δ under normal atmospheric pressure. The effects of B15C5 pendant and the length of chain bonded to B15C5 in these complexes on the O2-binding capabilities and oxidation for p-xylene were investigated with the comparison of crown-free analogues CoL^4 2.展开更多
A novel Pd(II) Benzo-15-crown-5 complex [Na(B15CS)]_2[Pd(SCN)_4] has been isolated and characterized by IR and X-ray diffraction analysis. The crystal structure belongs to monoclinic, space group P2_1,/n with cell dim...A novel Pd(II) Benzo-15-crown-5 complex [Na(B15CS)]_2[Pd(SCN)_4] has been isolated and characterized by IR and X-ray diffraction analysis. The crystal structure belongs to monoclinic, space group P2_1,/n with cell dimensions, a = l.0164(6), b = l.3743(3), c = l.4987(7) nm, β = 95.248(6) °, V = 2.0847 'nm_3, Z = 2, F(000) = 944, R = 0.053, Rw = 0.072. The compound consists of two [Na(B15CS)]+ complex canons and a [Pd(SCN)4_]^(2-) complex anion. Each sodium ion is coordinated by five crown ether oxygen atoms and one N atom from the SCN group of [Pd(SCN)_4]^(2-) to form stable neutral complex.展开更多
Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,B...Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.展开更多
The syntheses of a new type of heteromacrocyclic polyether- 2,3-benzo-1,4,7,13-tetraoxa-10-telluracyclopentadeca-2-ene(L),and its pla- tinum complex(PtL_2Cl_2)were described.The catalytic activity of this complex for ...The syntheses of a new type of heteromacrocyclic polyether- 2,3-benzo-1,4,7,13-tetraoxa-10-telluracyclopentadeca-2-ene(L),and its pla- tinum complex(PtL_2Cl_2)were described.The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.展开更多
The title complex (PtL_2Cl_2) was synthesized by reacting 10-selenabenzo-15-crown-5 (L) with potassium chloroplatinite. Its catalytic activity for the hydrosilylation of olefins by triethoxysilane, was investi gated.
ESR measurements have been carried out for some copper(Ⅱ) complexes of bis(4'-ben- zo-15-crown-5) at 77 K.The results of ESR spectrometric titration indicated that the binuclear com- plexes were prepared in the p...ESR measurements have been carried out for some copper(Ⅱ) complexes of bis(4'-ben- zo-15-crown-5) at 77 K.The results of ESR spectrometric titration indicated that the binuclear com- plexes were prepared in the present system.The binuclear complexes revealed characteristic ESR g-anisotropies (gZ<gX,gY) which are typical of the copper(Ⅱ) complexes with a 3d_Z^2 ground state doublet.However,in this case,the innermolecular copper(Ⅱ)-copper(Ⅱ) spin interaction was not observed.ESR measurements also showed that a small amount of the sandwich type copper(Ⅱ) com- plexes were formed in the presence of excess bis (4'-benzo-15-crown-5).A reasonable explanation was given for the ESR results.展开更多
[Na (N- (p-chlorophenyl ) aza-15--crown--5 ) (Et2O )]2 (Na2W0.5 Mo7.5 O26), Mr= 2119. 4, monoclinic, space group P21/c, a= 17. 803(4), b= 13. 674 (3), c= 14. 610(3), β= 112. 33(3)°, V=3290(1) A3, Z= 2, Dc= 2. 13...[Na (N- (p-chlorophenyl ) aza-15--crown--5 ) (Et2O )]2 (Na2W0.5 Mo7.5 O26), Mr= 2119. 4, monoclinic, space group P21/c, a= 17. 803(4), b= 13. 674 (3), c= 14. 610(3), β= 112. 33(3)°, V=3290(1) A3, Z= 2, Dc= 2. 139 g/cm3, μ= 1.704 mm-1, F (000) = 2079, R = 0. 026, Rw= 0. 030. The supermolecular complexconsists of one [Na2W0.5Mo7.5O28)2- anion in which only two Mo atoms are replaced byW in 25% (M= l/4W+3/4Mo) and the two Na+ are linked symmetrically to neighbouring [W0.5Mo7.5O26]4- units on the right and the left respectively and two complexcanons in which each Na+ deviates from the plane of the four ether oxygens and is coordinated to every hetero--atom in the crownether ring, and is also coordinated to the Oatom of Et2O.展开更多
Two novel benzo 15 crown 5 derivatives containing thiocycle(3) and selenacycle(4) have been synthesized in the presence of Na 2S·9H 2O or Na 2Se 2 and characterized by elemental analysis and mass, IR, UV and 1H N...Two novel benzo 15 crown 5 derivatives containing thiocycle(3) and selenacycle(4) have been synthesized in the presence of Na 2S·9H 2O or Na 2Se 2 and characterized by elemental analysis and mass, IR, UV and 1H NMR spectroscopy. The cation binding abilities and selectivities of parent benzo 15 crown 5(1) and its derivatives 3 and 4 with alkali and heavy metal ions have been evaluated by solvent extraction of aqueous metal picrates. The results obtained indicated that novel selera 3 cyclopentene[3,4 d]benzo 15 crown 5(4) showed moderate extractability and selectivity for Ag + over any other alkali and heavy metal ions. [WT5HZ]展开更多
基金The authors gratefully acknowledge the grants from the National Natural Science Foundation of China(No.20072025)Education 0ffice Foundation of Sichuan Province(No.2005C012)Sichuan Provincial Department of Science&Technology(No.2006J13-143)in support of this work.
文摘The oxygenation constants （Ko2） of cobalt（Ⅱ） hydroxamates （CoL^1 2-CoL^3 2） with benzo-15-crown-5 （B15C5） pendants were measured over the range of -5 to ＋20 ℃, and the values of thermodynamic parameters （ΔH^0 and ΔS^0） were calculated based on these （Ko2） values, Meanwhile, these crowned complexes were employed to the oxidation for p-xylene to p-toluic acid with air at 110Δ under normal atmospheric pressure. The effects of B15C5 pendant and the length of chain bonded to B15C5 in these complexes on the O2-binding capabilities and oxidation for p-xylene were investigated with the comparison of crown-free analogues CoL^4 2.
文摘A novel Pd(II) Benzo-15-crown-5 complex [Na(B15CS)]_2[Pd(SCN)_4] has been isolated and characterized by IR and X-ray diffraction analysis. The crystal structure belongs to monoclinic, space group P2_1,/n with cell dimensions, a = l.0164(6), b = l.3743(3), c = l.4987(7) nm, β = 95.248(6) °, V = 2.0847 'nm_3, Z = 2, F(000) = 944, R = 0.053, Rw = 0.072. The compound consists of two [Na(B15CS)]+ complex canons and a [Pd(SCN)4_]^(2-) complex anion. Each sodium ion is coordinated by five crown ether oxygen atoms and one N atom from the SCN group of [Pd(SCN)_4]^(2-) to form stable neutral complex.
基金the National Natural Science Foundation of China (No. 20371040) the Foundation (031-A21-004)of Gansu province and the Foundation (No. 02-18) of Northwest Normal University.
文摘Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.
文摘The syntheses of a new type of heteromacrocyclic polyether- 2,3-benzo-1,4,7,13-tetraoxa-10-telluracyclopentadeca-2-ene(L),and its pla- tinum complex(PtL_2Cl_2)were described.The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.
文摘The title complex (PtL_2Cl_2) was synthesized by reacting 10-selenabenzo-15-crown-5 (L) with potassium chloroplatinite. Its catalytic activity for the hydrosilylation of olefins by triethoxysilane, was investi gated.
文摘ESR measurements have been carried out for some copper(Ⅱ) complexes of bis(4'-ben- zo-15-crown-5) at 77 K.The results of ESR spectrometric titration indicated that the binuclear com- plexes were prepared in the present system.The binuclear complexes revealed characteristic ESR g-anisotropies (gZ<gX,gY) which are typical of the copper(Ⅱ) complexes with a 3d_Z^2 ground state doublet.However,in this case,the innermolecular copper(Ⅱ)-copper(Ⅱ) spin interaction was not observed.ESR measurements also showed that a small amount of the sandwich type copper(Ⅱ) com- plexes were formed in the presence of excess bis (4'-benzo-15-crown-5).A reasonable explanation was given for the ESR results.
文摘[Na (N- (p-chlorophenyl ) aza-15--crown--5 ) (Et2O )]2 (Na2W0.5 Mo7.5 O26), Mr= 2119. 4, monoclinic, space group P21/c, a= 17. 803(4), b= 13. 674 (3), c= 14. 610(3), β= 112. 33(3)°, V=3290(1) A3, Z= 2, Dc= 2. 139 g/cm3, μ= 1.704 mm-1, F (000) = 2079, R = 0. 026, Rw= 0. 030. The supermolecular complexconsists of one [Na2W0.5Mo7.5O28)2- anion in which only two Mo atoms are replaced byW in 25% (M= l/4W+3/4Mo) and the two Na+ are linked symmetrically to neighbouring [W0.5Mo7.5O26]4- units on the right and the left respectively and two complexcanons in which each Na+ deviates from the plane of the four ether oxygens and is coordinated to every hetero--atom in the crownether ring, and is also coordinated to the Oatom of Et2O.
文摘Two novel benzo 15 crown 5 derivatives containing thiocycle(3) and selenacycle(4) have been synthesized in the presence of Na 2S·9H 2O or Na 2Se 2 and characterized by elemental analysis and mass, IR, UV and 1H NMR spectroscopy. The cation binding abilities and selectivities of parent benzo 15 crown 5(1) and its derivatives 3 and 4 with alkali and heavy metal ions have been evaluated by solvent extraction of aqueous metal picrates. The results obtained indicated that novel selera 3 cyclopentene[3,4 d]benzo 15 crown 5(4) showed moderate extractability and selectivity for Ag + over any other alkali and heavy metal ions. [WT5HZ]
