The novel complexes, Cp(CO) 2FeTiCp 2Cl(1) and Cp(CO) 2FeSn(CH 2CMe 2Ph) 3(2), were synthesized and characterized by means of elemental analyses and IR spectra, Cp(CO) 2FeSn· (CH 2CMe 2Ph) 3 was addi...The novel complexes, Cp(CO) 2FeTiCp 2Cl(1) and Cp(CO) 2FeSn(CH 2CMe 2Ph) 3(2), were synthesized and characterized by means of elemental analyses and IR spectra, Cp(CO) 2FeSn· (CH 2CMe 2Ph) 3 was additionally characterized by X ray crystal structure analysis. The results of the elemental analyses are in good agreement with the theoretical values. The IR spectra show the existence of η 5 2,4 cyclopentadien 1 yl, carbonyl and methyl groups in the title complexes. The above experimental results show that the M-M bond exists in Cp(CO) 2FeSn· (CH 2Me 2Ph) 3, while the existence of the M-M bond in Cp(CO) 2FeTiCp 2Cl is highly possible, too. Both the two complexes are rather stable towards air and moisture, easily soluble in tetrahydrofuran and toluene, while their solubilities are greatly different in n hexane.展开更多
Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the...Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the structure and bonding in lanthanide and actinide metal complexes using 166Er, t55Gd, and 237Np Mtissbauer spectroscopies in connection with single-crystal and/or powder X-ray diffraction, making clear the differences on their structures as well as the differences in the participation of 4f and 5f orbitals in the chemical bonds. In this article, the crystal structures of two novel Gd（Ⅲ） acetylacetonato complexes, Gd（pta）3 · 2H2O （pta = 1,1,1 -trifluoro-5,5-dimethy 1-2,4-hexanedione） and Gd（bfa）3 · 2H2O （bfa = 1, 1, 1 -trifluoro-4-phenyl-2-4-butanedione） were reported. Though both of them were dihydrate and had distorted square antiprismatical structure, Gd（pta）3 · 2H2O crystallizes in the P 2 1/n （#14） monoclinic space group and its lattice parameters are a = 1.4141（6） nm, b = 1.0708（3） nm, c =2.2344（4） nm, β =952.4（2）°, and Gd（bfa）3· 2H2O crystallizes in P 212121 orthorhombic space group and its lattice parameters were a = 1.322 （1） nm, b = 2.295 （1） nm, c = 1. 0786（8） nm. In the meantime, the authors had finished a systematic investigation on the ^155Gd Mossbauer isomer shift （δ） of various Gd（Ⅲ） metal complexes having a different coordination number （C.N.） and different ratios coordinating oxygen to nitrogen. A tendency for the 6 value to decrease with an increase in the C.N, and the number of the nitrogen atom coordinating to Gd was confirmed. This indicated that the Gd-O and/or Gd-N bond in the investigated Gd（Ⅲ） metal complexes had a small covalent contribution, which was possible to be deduced from the O and/or N atoms of the lisands donating electrons to 6s, 5d, and 4f orbitals of Gd.展开更多
The anionic carbonyl complexes of groupsⅣandⅤmetals TM(CO)6,7(TM=Ti,Zr,Hf,V,Nb,Ta)are prepared in the gas phase using a laser vaporation-supersonic expansion ion source.The infrared spectra of TM(CO)_(6,7)-anion com...The anionic carbonyl complexes of groupsⅣandⅤmetals TM(CO)6,7(TM=Ti,Zr,Hf,V,Nb,Ta)are prepared in the gas phase using a laser vaporation-supersonic expansion ion source.The infrared spectra of TM(CO)_(6,7)-anion complexes in the carbonyl stretching frequency region are measured by mass-selected infrared photodissociation spectroscopy.The six-coordinated TM(CO)_(6)-anions are determined to be the coordination saturate complexes for both the groupⅣand groupⅤmetals.The TM(CO)_(6)-complexes of groupⅣmetals(TM=Ti,Zr,Hf)are 17-electron complexes having a~2A1gground state with D3dsymmetry,while the TM(CO)_(6)-complexes of groupⅤmetals(TM=Ⅴ,Nb,Ta)are 18-electron species with a closed-shell singlet ground state possessing Ohsymmetry.The energy decomposition analyses indicate that the metal-CO covalent bonding is dominated by TM-(d)→(CO)6π-backdonation and TM-(d)←(CO)6σ-donation interactions.展开更多
Novel 1,3-distal p-tert-butylcalix[4]arene Schiff bases were efficiently synthesized in three steps. At first p-tert-hutylcalix[4]arene was reacted with N-2-hydroxyethylphthalimide catalyzed by TPP/DEAD or alkylated w...Novel 1,3-distal p-tert-butylcalix[4]arene Schiff bases were efficiently synthesized in three steps. At first p-tert-hutylcalix[4]arene was reacted with N-2-hydroxyethylphthalimide catalyzed by TPP/DEAD or alkylated with ω-hatoalkylphthalimide in the system of K2CO3/KI/CH3COCH3 to give 1,3-distal diphthalimidoalkyl calixarenes, which were in turn hydrazinolyzed to give diaminoalkyl calixarenes. Then with the aid of the condensation of active calixarene amines with salicylaldehyde, 2-hydroxy-l-naphthaldehyde or pyridine-2-carboxaldehyde, a series of 1,3-distal calixarene Schiff bases was prepared in satisfied yields. The single crystal structures and complexing properties of these Schiff bases for transition metal ions were studied.展开更多
A novel hydrated cobalt tetraborate complex NH4[Co（NH3）5（H2O）] [B4O5（OH）4]2·6H2O, was synthesized by the reaction of NH4-borate aqueous with COC12 and its structure was determined by single crystal X-ray di...A novel hydrated cobalt tetraborate complex NH4[Co（NH3）5（H2O）] [B4O5（OH）4]2·6H2O, was synthesized by the reaction of NH4-borate aqueous with COC12 and its structure was determined by single crystal X-ray diffraction. The crystal system of this complex is orthorhombic, the space group is Pnma, and the unit cell parameters are a= 1.2901（2） nm, b= 1.6817（3） nm, c= 1.1368（2） nm, α=β=γ=90°, V=2.4742（8） nm3, and Z=4. This compound contains infinite borate layers constructed from [B4O5（OH）4]2 units via hydrogen bonds. The adjacent polyborate anion layers are further linked together with the octahedral [Co（NH3）5（H2O）]3＋ groups through hydrogen bonds to form 3D framework. The NH＋ groups and guest water molecules are deposited in the empty space of this framework and interact with the layers by extensive hydrogen bonds. Infrared and Raman spectra （4000--400 cm l） of NH4[Co（NH3）5（H20）][B4O5（OH）4]2·6H2O were recorded at room temperature and analyzed. Fundamental vibra- tional modes were identified and band assignments were made. The middle band observed at 575 cm^-1in Raman spectrum is the pulse vibration of [B4O5（OH）4]2-.展开更多
文摘The novel complexes, Cp(CO) 2FeTiCp 2Cl(1) and Cp(CO) 2FeSn(CH 2CMe 2Ph) 3(2), were synthesized and characterized by means of elemental analyses and IR spectra, Cp(CO) 2FeSn· (CH 2CMe 2Ph) 3 was additionally characterized by X ray crystal structure analysis. The results of the elemental analyses are in good agreement with the theoretical values. The IR spectra show the existence of η 5 2,4 cyclopentadien 1 yl, carbonyl and methyl groups in the title complexes. The above experimental results show that the M-M bond exists in Cp(CO) 2FeSn· (CH 2Me 2Ph) 3, while the existence of the M-M bond in Cp(CO) 2FeTiCp 2Cl is highly possible, too. Both the two complexes are rather stable towards air and moisture, easily soluble in tetrahydrofuran and toluene, while their solubilities are greatly different in n hexane.
基金Project supported by the Grants-in-Aid for Scientific Research from the Ministry of Education, Science and Culture, Japan andin Part by the Inter-University Joint Research Program for the Common Use of JAERI (Japan Atomic Energy Research Institute)Facilities
文摘Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the structure and bonding in lanthanide and actinide metal complexes using 166Er, t55Gd, and 237Np Mtissbauer spectroscopies in connection with single-crystal and/or powder X-ray diffraction, making clear the differences on their structures as well as the differences in the participation of 4f and 5f orbitals in the chemical bonds. In this article, the crystal structures of two novel Gd（Ⅲ） acetylacetonato complexes, Gd（pta）3 · 2H2O （pta = 1,1,1 -trifluoro-5,5-dimethy 1-2,4-hexanedione） and Gd（bfa）3 · 2H2O （bfa = 1, 1, 1 -trifluoro-4-phenyl-2-4-butanedione） were reported. Though both of them were dihydrate and had distorted square antiprismatical structure, Gd（pta）3 · 2H2O crystallizes in the P 2 1/n （#14） monoclinic space group and its lattice parameters are a = 1.4141（6） nm, b = 1.0708（3） nm, c =2.2344（4） nm, β =952.4（2）°, and Gd（bfa）3· 2H2O crystallizes in P 212121 orthorhombic space group and its lattice parameters were a = 1.322 （1） nm, b = 2.295 （1） nm, c = 1. 0786（8） nm. In the meantime, the authors had finished a systematic investigation on the ^155Gd Mossbauer isomer shift （δ） of various Gd（Ⅲ） metal complexes having a different coordination number （C.N.） and different ratios coordinating oxygen to nitrogen. A tendency for the 6 value to decrease with an increase in the C.N, and the number of the nitrogen atom coordinating to Gd was confirmed. This indicated that the Gd-O and/or Gd-N bond in the investigated Gd（Ⅲ） metal complexes had a small covalent contribution, which was possible to be deduced from the O and/or N atoms of the lisands donating electrons to 6s, 5d, and 4f orbitals of Gd.
基金supported by the National Natural Science Foundation of China(No.21873020 and No.21688102)。
文摘The anionic carbonyl complexes of groupsⅣandⅤmetals TM(CO)6,7(TM=Ti,Zr,Hf,V,Nb,Ta)are prepared in the gas phase using a laser vaporation-supersonic expansion ion source.The infrared spectra of TM(CO)_(6,7)-anion complexes in the carbonyl stretching frequency region are measured by mass-selected infrared photodissociation spectroscopy.The six-coordinated TM(CO)_(6)-anions are determined to be the coordination saturate complexes for both the groupⅣand groupⅤmetals.The TM(CO)_(6)-complexes of groupⅣmetals(TM=Ti,Zr,Hf)are 17-electron complexes having a~2A1gground state with D3dsymmetry,while the TM(CO)_(6)-complexes of groupⅤmetals(TM=Ⅴ,Nb,Ta)are 18-electron species with a closed-shell singlet ground state possessing Ohsymmetry.The energy decomposition analyses indicate that the metal-CO covalent bonding is dominated by TM-(d)→(CO)6π-backdonation and TM-(d)←(CO)6σ-donation interactions.
基金Supported by the National Natural Science Foundation of China(No.20672091)
文摘Novel 1,3-distal p-tert-butylcalix[4]arene Schiff bases were efficiently synthesized in three steps. At first p-tert-hutylcalix[4]arene was reacted with N-2-hydroxyethylphthalimide catalyzed by TPP/DEAD or alkylated with ω-hatoalkylphthalimide in the system of K2CO3/KI/CH3COCH3 to give 1,3-distal diphthalimidoalkyl calixarenes, which were in turn hydrazinolyzed to give diaminoalkyl calixarenes. Then with the aid of the condensation of active calixarene amines with salicylaldehyde, 2-hydroxy-l-naphthaldehyde or pyridine-2-carboxaldehyde, a series of 1,3-distal calixarene Schiff bases was prepared in satisfied yields. The single crystal structures and complexing properties of these Schiff bases for transition metal ions were studied.
文摘A novel hydrated cobalt tetraborate complex NH4[Co（NH3）5（H2O）] [B4O5（OH）4]2·6H2O, was synthesized by the reaction of NH4-borate aqueous with COC12 and its structure was determined by single crystal X-ray diffraction. The crystal system of this complex is orthorhombic, the space group is Pnma, and the unit cell parameters are a= 1.2901（2） nm, b= 1.6817（3） nm, c= 1.1368（2） nm, α=β=γ=90°, V=2.4742（8） nm3, and Z=4. This compound contains infinite borate layers constructed from [B4O5（OH）4]2 units via hydrogen bonds. The adjacent polyborate anion layers are further linked together with the octahedral [Co（NH3）5（H2O）]3＋ groups through hydrogen bonds to form 3D framework. The NH＋ groups and guest water molecules are deposited in the empty space of this framework and interact with the layers by extensive hydrogen bonds. Infrared and Raman spectra （4000--400 cm l） of NH4[Co（NH3）5（H20）][B4O5（OH）4]2·6H2O were recorded at room temperature and analyzed. Fundamental vibra- tional modes were identified and band assignments were made. The middle band observed at 575 cm^-1in Raman spectrum is the pulse vibration of [B4O5（OH）4]2-.
