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
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
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
Novel unsymmetrical bissalicylaldimine bis-Schiff bases with a benzo-10-aza-15-crown-5 pendant and their cobalt complexes have been synthesized via condensation of 3 or 5-[（benzo-10-aza-15-crown-5）-10-ylmethyl] sali...Novel unsymmetrical bissalicylaldimine bis-Schiff bases with a benzo-10-aza-15-crown-5 pendant and their cobalt complexes have been synthesized via condensation of 3 or 5-[（benzo-10-aza-15-crown-5）-10-ylmethyl] salicylaldehyde with the half unit Schiff bases and characterized by ^1H NMR, IR, mass spectroscopy, elemental analysis, molar conductances and molar magnetic susceptibility.展开更多
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
Based on the 1,3-dipolar cycloaddition of azomethine ylide generated in situ from aldehyde and sarcosine attached to C60,two novel benzo-15-crown-5/C60 dyads with a different linking chain in each were designed and sy...Based on the 1,3-dipolar cycloaddition of azomethine ylide generated in situ from aldehyde and sarcosine attached to C60,two novel benzo-15-crown-5/C60 dyads with a different linking chain in each were designed and synthesized in yields of 30％ and 38％,respectively.It was found that their UV-Vis absorption spectra could be regulated hypsochromically by metal ions complexed.The long and soft linking chain was favorable for cooperate interaction of crown ether unit and C60 unit.展开更多
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 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.
基金Prgject supported by the National Natural Science Foundation of China （No. 29572059, and Key Project of Sichuan Province Education 0ffice （No. 2005D007）.
文摘Novel unsymmetrical bissalicylaldimine bis-Schiff bases with a benzo-10-aza-15-crown-5 pendant and their cobalt complexes have been synthesized via condensation of 3 or 5-[（benzo-10-aza-15-crown-5）-10-ylmethyl] salicylaldehyde with the half unit Schiff bases and characterized by ^1H NMR, IR, mass spectroscopy, elemental analysis, molar conductances and molar magnetic susceptibility.
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.
基金Supported by the Program for Innovative Research Team in Science and Technology in Fujian Province University,China,the Fujian Natural Science Foundation of China（No.2011J01031）,the Project of Fujian Provincial Department of Education,China（No.JA11044） and the Program for Excellent Young Researchers in University of Fujian Province,China（No.JA10056）.
文摘Based on the 1,3-dipolar cycloaddition of azomethine ylide generated in situ from aldehyde and sarcosine attached to C60,two novel benzo-15-crown-5/C60 dyads with a different linking chain in each were designed and synthesized in yields of 30％ and 38％,respectively.It was found that their UV-Vis absorption spectra could be regulated hypsochromically by metal ions complexed.The long and soft linking chain was favorable for cooperate interaction of crown ether unit and C60 unit.
