The evolved gaseous analysis (EGA),infrared spectra,and XRD have been applied to the study of solid state reactions of KSCN with five cobalt(Ⅲ)-ammine complexes:[Co- (NH_3)_5N_3]Cl_2,[Co(NH_3)_5(NO_2)]Cl_2,[Co(NH_3)_...The evolved gaseous analysis (EGA),infrared spectra,and XRD have been applied to the study of solid state reactions of KSCN with five cobalt(Ⅲ)-ammine complexes:[Co- (NH_3)_5N_3]Cl_2,[Co(NH_3)_5(NO_2)]Cl_2,[Co(NH_3)_5(H_2O)]Cl_3,[Co(NH_3)_5Cl]Cl_2,and [Co(NH_3)_6]Cl_3 in a hydrogen atmosphere.It is found that the existence of KSCN shifts the thermal decom- position of these complexes to a lower temperature.The corresponding peak temperatures are near 140℃.The effect of KSCN is discussed and kinetic parameters of deammine reactions are calculated.展开更多
The novel three-dimension edta-linked （edta--ethylenediamine-N,N,N＇,N＇-tetraacetate） heterometallic complex [Sba（edta）2-μ4-Co（H20）2]·5.15H2O has been synthesized and characterized by elemental analyses, ...The novel three-dimension edta-linked （edta--ethylenediamine-N,N,N＇,N＇-tetraacetate） heterometallic complex [Sba（edta）2-μ4-Co（H20）2]·5.15H2O has been synthesized and characterized by elemental analyses, FT-IR spectrum, X-ray diffraction analyses and thermogravimetry-differential scanning calorimetry （TG-DSC）. The complex crys- tallizes in the monoclinic system, space group P21/n, lattice parameters： a=0.69969（2） nm, b=2.08705（4） nm, c-- 1.08106（2） nm, β=90.031（1）°, V=1.57866（6） nm3, Z=2, Mr=1007.76, Dc=2.120 g-cm 3 F（000）=1001,μ= 2.323 mm t, the final R=0.0235 and wR--0.0629 for 3480 observed reflections [l〉2σ（l）]. In the structure each Co（II） ion is connected with Sb（III） ions bridging by four carboxylic oxygen atoms, and in each [Sb（edta）] anion, the Sb（III） ion is six coordinated by two nitrogen and four oxygen from edta ions, together with a lone electron pair at the equatorial position. In the complex, the coordination number of Co（II） ion is six and its coordination environment is composed of four carboxylic oxygen atoms from four different edta ions and two oxygen atoms from two H2O molecules. The degradation of the sample proceeds in several steps and the water molecules and ligands are successively emited.展开更多
The monomeric cobalt-phosphite-thiolato complex [ Co (mpt)2 {P (OCH3 )3 }2 ] BF4 (Hmpt = 2-mercaptothiazoline) has been prepared and characterized by X-ray crystallography. The complex crystallizes in the monoclinic s...The monomeric cobalt-phosphite-thiolato complex [ Co (mpt)2 {P (OCH3 )3 }2 ] BF4 (Hmpt = 2-mercaptothiazoline) has been prepared and characterized by X-ray crystallography. The complex crystallizes in the monoclinic space group C2/c with a= 0.8078(5), b=2.6020(18), c=1.2191(7) nm, β= 99.38 (1)°, V= 2.528(3) nm3, and Z = 4. The structure comprises discrete cations [Co(mpt)2{P(OCH3)3}2.] + and anions BF4- , in which the cobalt (Ⅲ) atom is coordinated to two chelate mpt- and two as-oriented monodentate P(OCH3)3 ligands in a highly distorted octahedral geometry. The most distorted angles are S(2)-Co(1)-S(2a) of 162.23(10)° and N(1)-Co(1)-S(2) of 71. 47 (13)°, the latter is caused by the geometric constraint of the bidentate ligand mpt- . Cyclic voltammetry has been used to study the electrochemical behavior of the title complex on the R electrode in MeCN solution with 0.1 mol·L-1 of Bun4NBF4 as electrolyte. The results indicate that the title complex is unstable in MeCN.展开更多
文摘The evolved gaseous analysis (EGA),infrared spectra,and XRD have been applied to the study of solid state reactions of KSCN with five cobalt(Ⅲ)-ammine complexes:[Co- (NH_3)_5N_3]Cl_2,[Co(NH_3)_5(NO_2)]Cl_2,[Co(NH_3)_5(H_2O)]Cl_3,[Co(NH_3)_5Cl]Cl_2,and [Co(NH_3)_6]Cl_3 in a hydrogen atmosphere.It is found that the existence of KSCN shifts the thermal decom- position of these complexes to a lower temperature.The corresponding peak temperatures are near 140℃.The effect of KSCN is discussed and kinetic parameters of deammine reactions are calculated.
文摘The novel three-dimension edta-linked （edta--ethylenediamine-N,N,N＇,N＇-tetraacetate） heterometallic complex [Sba（edta）2-μ4-Co（H20）2]·5.15H2O has been synthesized and characterized by elemental analyses, FT-IR spectrum, X-ray diffraction analyses and thermogravimetry-differential scanning calorimetry （TG-DSC）. The complex crys- tallizes in the monoclinic system, space group P21/n, lattice parameters： a=0.69969（2） nm, b=2.08705（4） nm, c-- 1.08106（2） nm, β=90.031（1）°, V=1.57866（6） nm3, Z=2, Mr=1007.76, Dc=2.120 g-cm 3 F（000）=1001,μ= 2.323 mm t, the final R=0.0235 and wR--0.0629 for 3480 observed reflections [l〉2σ（l）]. In the structure each Co（II） ion is connected with Sb（III） ions bridging by four carboxylic oxygen atoms, and in each [Sb（edta）] anion, the Sb（III） ion is six coordinated by two nitrogen and four oxygen from edta ions, together with a lone electron pair at the equatorial position. In the complex, the coordination number of Co（II） ion is six and its coordination environment is composed of four carboxylic oxygen atoms from four different edta ions and two oxygen atoms from two H2O molecules. The degradation of the sample proceeds in several steps and the water molecules and ligands are successively emited.
基金Project supported by the National Natural Science Foundation of China (No. 29671035)the Natural Science Foundation of Guangdong Province (No. 970155),the State Key laboratory of Structural Chemistry.
文摘The monomeric cobalt-phosphite-thiolato complex [ Co (mpt)2 {P (OCH3 )3 }2 ] BF4 (Hmpt = 2-mercaptothiazoline) has been prepared and characterized by X-ray crystallography. The complex crystallizes in the monoclinic space group C2/c with a= 0.8078(5), b=2.6020(18), c=1.2191(7) nm, β= 99.38 (1)°, V= 2.528(3) nm3, and Z = 4. The structure comprises discrete cations [Co(mpt)2{P(OCH3)3}2.] + and anions BF4- , in which the cobalt (Ⅲ) atom is coordinated to two chelate mpt- and two as-oriented monodentate P(OCH3)3 ligands in a highly distorted octahedral geometry. The most distorted angles are S(2)-Co(1)-S(2a) of 162.23(10)° and N(1)-Co(1)-S(2) of 71. 47 (13)°, the latter is caused by the geometric constraint of the bidentate ligand mpt- . Cyclic voltammetry has been used to study the electrochemical behavior of the title complex on the R electrode in MeCN solution with 0.1 mol·L-1 of Bun4NBF4 as electrolyte. The results indicate that the title complex is unstable in MeCN.
