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
Thermodynamic parameters of complexation of naphto- 15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect...Thermodynamic parameters of complexation of naphto- 15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect and entropy effect of the complexation is discussed on the basis of the guest ions structure and the solvent effect. The stability constants tendency to vary with ion radius was interpreted. Complex of naphtha-15-crown-5 with calcium ion is very stable due to the synergism of static electric interaction and size selectivity between the host and the guest.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 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
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 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.
[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
The complex [Na(15-crown-5)] [Cd(SCN)3] (15-crown-5 = C10H20 O5) crysializes in monoclinic space group P21/c with a=10. 219(2) ,b= 10. 575(2) ,c= 20. 572(2) A ,β=98. 45(1)°,V= 2198. 7A3,Mr=529. 89,Z = 4,Dx=1. 60...The complex [Na(15-crown-5)] [Cd(SCN)3] (15-crown-5 = C10H20 O5) crysializes in monoclinic space group P21/c with a=10. 219(2) ,b= 10. 575(2) ,c= 20. 572(2) A ,β=98. 45(1)°,V= 2198. 7A3,Mr=529. 89,Z = 4,Dx=1. 600g/cm3,F (000) -1052,μ= 15. 708cm-1. The structure was solved by direct methods with the final R=0. 064. Results of structure analysis indicate that the Na ion is bonded by 15-crown-5 to form a complex cation and the Cd(Ⅱ) is bonded by six SCN ion to form an anion chain with a distorted octahedral coordination.展开更多
The crystal and molecular structure of the title compound K(C14 H20O5)2AuCl4 has been determined by X-ray diffraction method.The crystallographic data are as follows;Mr=914.51,triclinic,space group P1,a=10.988(2),b=13...The crystal and molecular structure of the title compound K(C14 H20O5)2AuCl4 has been determined by X-ray diffraction method.The crystallographic data are as follows;Mr=914.51,triclinic,space group P1,a=10.988(2),b=13.472(4),c=13.696(2)A,α=77.72(1),β=79.02(2),γ=64.92(2)°,V=1782.6(4)A3,Z=2,Dc=1.704 g.cm-3,μ=45.858 cm-1,F(000)=454,R=0.019,Rw=0.018 for 5697 observed reflections with I≥3σ(I).X-ray structure determination shows that benzo-15-crown-5(B15C5)forms a 2:1 complex with KAu-C14 in which K+is sandwiched between two crown rings.The dihedral angle between these two ether oxygen planes is 11.9°.The anion AuCl4-has a planar square configuration which is bound with the complex cation K(B15C5)2+by electrostatic force to form an ion-pair.展开更多
Crystal structure of the title compound C 16 H 25 O 2NS 2 has been determined by X-ray diffraction method. Its crystallographic data were as follows: M r=327.51, triclinic, space group P1, a=8.864(3), b=10.127(4), c=1...Crystal structure of the title compound C 16 H 25 O 2NS 2 has been determined by X-ray diffraction method. Its crystallographic data were as follows: M r=327.51, triclinic, space group P1, a=8.864(3), b=10.127(4), c=10.390(3) , α=105.94(3), β=103.10(2), γ=90.96(3)°, V=870.3(7) 3, Z=2, D c=1.250g.cm -3 , μ(MoKα)=2.966cm -1 , F(000)=176, a total of 3275 reflections measured (2θ max =50°), 2246[I5σ(I)] used in the refinement, R=0.067, R w=0.082. The result shows that the distances of N(1)-C(2) and N(1)-C(3) are longer than that of N(1)-C(11), which indicates that the interaction of C Ar -N sp 2 is stronger than that of C sp 3 -N sp 2 . Oxygen, nitrogen and sulfur atoms of the ring in the same plane was deduced from the least\|squares planes and the dihedral angles.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Thermodynamic parameters of complexation of naphto- 15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect and entropy effect of the complexation is discussed on the basis of the guest ions structure and the solvent effect. The stability constants tendency to vary with ion radius was interpreted. Complex of naphtha-15-crown-5 with calcium ion is very stable due to the synergism of static electric interaction and size selectivity between the host and the guest.
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.
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 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[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.
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The complex [Na(15-crown-5)] [Cd(SCN)3] (15-crown-5 = C10H20 O5) crysializes in monoclinic space group P21/c with a=10. 219(2) ,b= 10. 575(2) ,c= 20. 572(2) A ,β=98. 45(1)°,V= 2198. 7A3,Mr=529. 89,Z = 4,Dx=1. 600g/cm3,F (000) -1052,μ= 15. 708cm-1. The structure was solved by direct methods with the final R=0. 064. Results of structure analysis indicate that the Na ion is bonded by 15-crown-5 to form a complex cation and the Cd(Ⅱ) is bonded by six SCN ion to form an anion chain with a distorted octahedral coordination.
文摘The crystal and molecular structure of the title compound K(C14 H20O5)2AuCl4 has been determined by X-ray diffraction method.The crystallographic data are as follows;Mr=914.51,triclinic,space group P1,a=10.988(2),b=13.472(4),c=13.696(2)A,α=77.72(1),β=79.02(2),γ=64.92(2)°,V=1782.6(4)A3,Z=2,Dc=1.704 g.cm-3,μ=45.858 cm-1,F(000)=454,R=0.019,Rw=0.018 for 5697 observed reflections with I≥3σ(I).X-ray structure determination shows that benzo-15-crown-5(B15C5)forms a 2:1 complex with KAu-C14 in which K+is sandwiched between two crown rings.The dihedral angle between these two ether oxygen planes is 11.9°.The anion AuCl4-has a planar square configuration which is bound with the complex cation K(B15C5)2+by electrostatic force to form an ion-pair.
文摘Crystal structure of the title compound C 16 H 25 O 2NS 2 has been determined by X-ray diffraction method. Its crystallographic data were as follows: M r=327.51, triclinic, space group P1, a=8.864(3), b=10.127(4), c=10.390(3) , α=105.94(3), β=103.10(2), γ=90.96(3)°, V=870.3(7) 3, Z=2, D c=1.250g.cm -3 , μ(MoKα)=2.966cm -1 , F(000)=176, a total of 3275 reflections measured (2θ max =50°), 2246[I5σ(I)] used in the refinement, R=0.067, R w=0.082. The result shows that the distances of N(1)-C(2) and N(1)-C(3) are longer than that of N(1)-C(11), which indicates that the interaction of C Ar -N sp 2 is stronger than that of C sp 3 -N sp 2 . Oxygen, nitrogen and sulfur atoms of the ring in the same plane was deduced from the least\|squares planes and the dihedral angles.
