The electrophilic substitution reaction occurring to the chelate ring of the complexes could be regarded as an indication of quasi-aromaticity of the ring systems, no catalyst was used and only triethylamine was emplo...The electrophilic substitution reaction occurring to the chelate ring of the complexes could be regarded as an indication of quasi-aromaticity of the ring systems, no catalyst was used and only triethylamine was employed, implying that the aroylating agents with different p-substituents are polarized enough to be effective electrophiles to attack the methine carbon of the electron-rich substrate 1. This property is probably the clue to polarization of the ligand electrons by the nickel( Ⅱ ) ion and to the participation of the nickel( Ⅱ ) in the π-bond systems of the two coordinated conjugated rings. The linearity relationship between vd-d maxima, E1/2OX(1) and σp are obtained, respectively. The electronic environment of central metal ion as well as the aromaticity of the ring system are affected by the electronic properties of the p-substituents. A comparison of the electrochemical results with each other showed .that when the electronegativity of the substituent was higher, the oxidation(Ni2+/Ni3+) becomes more difficult.展开更多
The kinetics of the reaction of [Ni(PnAO)—6H]° with formaldehyde was studied in H_2O—CH_3OH solution under neutral condition and a complicated mechanism with three steps including competitive, consecutive and r...The kinetics of the reaction of [Ni(PnAO)—6H]° with formaldehyde was studied in H_2O—CH_3OH solution under neutral condition and a complicated mechanism with three steps including competitive, consecutive and reverse reactions was proposed.展开更多
The available literature revealed a gap in reporting the rough rice drying kinetics parameters under isothermal conditions, particularly for Arkansas medium- and long-grain varieties. Therefore, medium-grain (RO170112...The available literature revealed a gap in reporting the rough rice drying kinetics parameters under isothermal conditions, particularly for Arkansas medium- and long-grain varieties. Therefore, medium-grain (RO170112 and Titan) and the long-grain (Diamond and Wells) rough rice varieties were dried under isothermal conditions. The drying process occurred under 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, and 100°C in a system emulating the thermogravimetric analyzer. Drying kinetics models were studied for four well-known models: Page, Newton, Logarithmic, and Henderson & Pabis. The drying kinetics constants were determined for the four studied models. The initial moisture content of rough rice was 28.2% db. Profound moisture reduction was observed during the first three hours of drying, followed by less moisture content reduction. The results showed that at the drying temperature of 100°C and after 6 hours of the drying process, the lowest moisture content reached 13.9% (db) for Titan rough rice. The drying rate of rough rice ranged between 7.41 and 2.01%/h during the first hour of drying under the studied temperature range of 40°C to 100°C. The drying rate was higher with the higher temperature levels during the first three hours. Among all the studied models, the Page, Newton, and Logarithmic models best fit 25%, 25%, and 50% of the twenty-eight studied cases. The challenge that arose from these results led to evolving a mathematical solution by joining the three models in one equation. The combined model showed the best fit for all the studied cases, with R<sup>2</sup> ranging between 0.9999 and 0.9954 for the medium- and long-grain rice varieties. Increasing the drying temperature increased the effective moisture diffusivity values. The highest effective moisture diffusivity of 18.104 × 10<sup>-9</sup> m<sup>2</sup>/s was obtained at the drying temperature of 100°C for medium-grain rice, Titan. The activation energy values ranged between 17.77 and 24.48 kJ/mol for the four rough rice varieties.展开更多
The localized molecular orbitals and energy levels for [Co_6 (μ_3-S)_8 (PH_3)_6] ̄(n+)(n=0, 1) as model molecules of the electron-rich [Co_6 (μ_3-S)_8 (PPh_3)_6] ̄(n+) (n=0,1) cluster compounds have been calculated ...The localized molecular orbitals and energy levels for [Co_6 (μ_3-S)_8 (PH_3)_6] ̄(n+)(n=0, 1) as model molecules of the electron-rich [Co_6 (μ_3-S)_8 (PPh_3)_6] ̄(n+) (n=0,1) cluster compounds have been calculated by using Edmiston-Ruedenberg energy localization scheme under the spin-unrestricted CNDO/2 approximation. It is shown that the cluster skeletons of these two isostructural molecules consist of the edge-localized two-centered two-electron (Co-S) bonds plus a pair of the skeleton electrons delocalized on the whole cluster core,leading an extra stability of the cluster core.The one-electron oxidation for the neutral molecule gives rise to a one-electron σ (Co-Co) bond.which further resonates among the three diagonal lines of the {Co_6} octahedron. The comparison between [Co_6 (μ_3-S)_8(PPh_3)_6] and [Co_6(μ_3-CO)_8(CO)_6] ̄(4-) indicates that the latter possesses face-localized bridging-bonds which are further delocalized on the whole surface of the cluster octahedron by the back-donation bonds from the lone electron pairs on the Co atoms to the capping carbonyl CO ligands. The structural features of the series of the [Co6(μ_3-X)_8L_6] ̄(n+)(X =S, Se; L=PPh_3,PEt_3, CO;n=0, 1) cluster compounds are briefly rationalized on the basis of the localization description as well.展开更多
The energy-localized CNDO/2 molecular orbitals have been calculated for the cluster anions of [Co_6 (CO)_(14)] ̄(4-) and [Ni_2Co_4 (CO)_(14)] ̄(2-)in order to get a deeper insight into the nature of their skeletal bon...The energy-localized CNDO/2 molecular orbitals have been calculated for the cluster anions of [Co_6 (CO)_(14)] ̄(4-) and [Ni_2Co_4 (CO)_(14)] ̄(2-)in order to get a deeper insight into the nature of their skeletal bonding. The bonding characteristics of these hexanuclear carbonyl cobaltates are described from a localization bonding viewpoint. There are two typical M-CO bondings, one of which is formed by electron donation from the terminal and capping carbonyl ligands into the vacant hybrid orbitals on the metal atoms , leading to formation ofσ(C_t→Co) and σ(C_b→{Co_3})bonds. The other typical M-CO bonding is back donation of the lone d-electron pairs on the metal atoms into the carbonyl ligands, forming π(Co→C_t) bonds, σ(Co→{C_(b2)}) bonds and π(Co→{C_(b4)} ) bonds. It is found that there are no direct metalmetal bondings in the skeletons of these two cluster anions.The delocalization situation of the skeletal bonding electrons is briefly discussed.展开更多
The wave functions, level energies and Mulliken population analysis of localized molecular orbitals (LMO's) for B4Cl4, 1,5-C2B3H5 and the closo-BnHn2- (n = 6-10, 12) are calculated by using the Edmiston-Reudenberg...The wave functions, level energies and Mulliken population analysis of localized molecular orbitals (LMO's) for B4Cl4, 1,5-C2B3H5 and the closo-BnHn2- (n = 6-10, 12) are calculated by using the Edmiston-Reudenberg energy localization scheme under the CNDO/2 approximation in order to reveal the nature of quasi-aromaticity of the closo-BnHn2- (n > 5). It has been found that all the B-H or B-Cl LMO's are highly localized between the B and H (or Cl) atoms, corresponding to B-H or B-Cl o-bond, while the Bn framework bonding is formed mainly by the three-centered two-electron B-B-B bonds on the polyhedral faces. In the cases of B4Cl4 and 1,5-C2B3H5, these three-centered B-B-B bonds just fill their polyhedral faces; however, for the framework bonding of the closo-BnHn2- (n > 5), the valence electron deficiency leads to the delocalization of their three-centered B-B-B bonds, and as delocalizability of this three-centered B-B-B bond increases, some three-centered B-B-B bonds are further delocalized to become a four-centered B-B-B-B bond. It is important that for the cioao-BnHn2- (n > 5), the sequence of this delocalizability of the three-centered B-B-B bond is consistent with the degree of quasi-aromaticity of the closo-boranes.展开更多
1 History of discovery of the low temperature phase barium metaborate (BBO)——an excel-lent new-type ultraviolet radiation frequency-doubling crystalline materialTHE first laser excitation in 1960 with ruby (α-Al...1 History of discovery of the low temperature phase barium metaborate (BBO)——an excel-lent new-type ultraviolet radiation frequency-doubling crystalline materialTHE first laser excitation in 1960 with ruby (α-Al<sub>2</sub>O<sub>3</sub>: Cr) as a laser crystal and the first dou-bling of frequency (347. 15 nm) in 1961 by irradiating quartz crystal (α-SiO<sub>2</sub>) with a 694. 3nm laser beam have laid the basis for the study of laser and nonlinear optical (NLO) crystals,展开更多
基金Supported by the National Natural Science Foundation of China
文摘The electrophilic substitution reaction occurring to the chelate ring of the complexes could be regarded as an indication of quasi-aromaticity of the ring systems, no catalyst was used and only triethylamine was employed, implying that the aroylating agents with different p-substituents are polarized enough to be effective electrophiles to attack the methine carbon of the electron-rich substrate 1. This property is probably the clue to polarization of the ligand electrons by the nickel( Ⅱ ) ion and to the participation of the nickel( Ⅱ ) in the π-bond systems of the two coordinated conjugated rings. The linearity relationship between vd-d maxima, E1/2OX(1) and σp are obtained, respectively. The electronic environment of central metal ion as well as the aromaticity of the ring system are affected by the electronic properties of the p-substituents. A comparison of the electrochemical results with each other showed .that when the electronegativity of the substituent was higher, the oxidation(Ni2+/Ni3+) becomes more difficult.
文摘The kinetics of the reaction of [Ni(PnAO)—6H]° with formaldehyde was studied in H_2O—CH_3OH solution under neutral condition and a complicated mechanism with three steps including competitive, consecutive and reverse reactions was proposed.
文摘The available literature revealed a gap in reporting the rough rice drying kinetics parameters under isothermal conditions, particularly for Arkansas medium- and long-grain varieties. Therefore, medium-grain (RO170112 and Titan) and the long-grain (Diamond and Wells) rough rice varieties were dried under isothermal conditions. The drying process occurred under 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, and 100°C in a system emulating the thermogravimetric analyzer. Drying kinetics models were studied for four well-known models: Page, Newton, Logarithmic, and Henderson & Pabis. The drying kinetics constants were determined for the four studied models. The initial moisture content of rough rice was 28.2% db. Profound moisture reduction was observed during the first three hours of drying, followed by less moisture content reduction. The results showed that at the drying temperature of 100°C and after 6 hours of the drying process, the lowest moisture content reached 13.9% (db) for Titan rough rice. The drying rate of rough rice ranged between 7.41 and 2.01%/h during the first hour of drying under the studied temperature range of 40°C to 100°C. The drying rate was higher with the higher temperature levels during the first three hours. Among all the studied models, the Page, Newton, and Logarithmic models best fit 25%, 25%, and 50% of the twenty-eight studied cases. The challenge that arose from these results led to evolving a mathematical solution by joining the three models in one equation. The combined model showed the best fit for all the studied cases, with R<sup>2</sup> ranging between 0.9999 and 0.9954 for the medium- and long-grain rice varieties. Increasing the drying temperature increased the effective moisture diffusivity values. The highest effective moisture diffusivity of 18.104 × 10<sup>-9</sup> m<sup>2</sup>/s was obtained at the drying temperature of 100°C for medium-grain rice, Titan. The activation energy values ranged between 17.77 and 24.48 kJ/mol for the four rough rice varieties.
文摘The localized molecular orbitals and energy levels for [Co_6 (μ_3-S)_8 (PH_3)_6] ̄(n+)(n=0, 1) as model molecules of the electron-rich [Co_6 (μ_3-S)_8 (PPh_3)_6] ̄(n+) (n=0,1) cluster compounds have been calculated by using Edmiston-Ruedenberg energy localization scheme under the spin-unrestricted CNDO/2 approximation. It is shown that the cluster skeletons of these two isostructural molecules consist of the edge-localized two-centered two-electron (Co-S) bonds plus a pair of the skeleton electrons delocalized on the whole cluster core,leading an extra stability of the cluster core.The one-electron oxidation for the neutral molecule gives rise to a one-electron σ (Co-Co) bond.which further resonates among the three diagonal lines of the {Co_6} octahedron. The comparison between [Co_6 (μ_3-S)_8(PPh_3)_6] and [Co_6(μ_3-CO)_8(CO)_6] ̄(4-) indicates that the latter possesses face-localized bridging-bonds which are further delocalized on the whole surface of the cluster octahedron by the back-donation bonds from the lone electron pairs on the Co atoms to the capping carbonyl CO ligands. The structural features of the series of the [Co6(μ_3-X)_8L_6] ̄(n+)(X =S, Se; L=PPh_3,PEt_3, CO;n=0, 1) cluster compounds are briefly rationalized on the basis of the localization description as well.
文摘The energy-localized CNDO/2 molecular orbitals have been calculated for the cluster anions of [Co_6 (CO)_(14)] ̄(4-) and [Ni_2Co_4 (CO)_(14)] ̄(2-)in order to get a deeper insight into the nature of their skeletal bonding. The bonding characteristics of these hexanuclear carbonyl cobaltates are described from a localization bonding viewpoint. There are two typical M-CO bondings, one of which is formed by electron donation from the terminal and capping carbonyl ligands into the vacant hybrid orbitals on the metal atoms , leading to formation ofσ(C_t→Co) and σ(C_b→{Co_3})bonds. The other typical M-CO bonding is back donation of the lone d-electron pairs on the metal atoms into the carbonyl ligands, forming π(Co→C_t) bonds, σ(Co→{C_(b2)}) bonds and π(Co→{C_(b4)} ) bonds. It is found that there are no direct metalmetal bondings in the skeletons of these two cluster anions.The delocalization situation of the skeletal bonding electrons is briefly discussed.
基金Project supported by the National Natural Science Foundation of China and the Fujian NaturalScience Foundation.
文摘The wave functions, level energies and Mulliken population analysis of localized molecular orbitals (LMO's) for B4Cl4, 1,5-C2B3H5 and the closo-BnHn2- (n = 6-10, 12) are calculated by using the Edmiston-Reudenberg energy localization scheme under the CNDO/2 approximation in order to reveal the nature of quasi-aromaticity of the closo-BnHn2- (n > 5). It has been found that all the B-H or B-Cl LMO's are highly localized between the B and H (or Cl) atoms, corresponding to B-H or B-Cl o-bond, while the Bn framework bonding is formed mainly by the three-centered two-electron B-B-B bonds on the polyhedral faces. In the cases of B4Cl4 and 1,5-C2B3H5, these three-centered B-B-B bonds just fill their polyhedral faces; however, for the framework bonding of the closo-BnHn2- (n > 5), the valence electron deficiency leads to the delocalization of their three-centered B-B-B bonds, and as delocalizability of this three-centered B-B-B bond increases, some three-centered B-B-B bonds are further delocalized to become a four-centered B-B-B-B bond. It is important that for the cioao-BnHn2- (n > 5), the sequence of this delocalizability of the three-centered B-B-B bond is consistent with the degree of quasi-aromaticity of the closo-boranes.
文摘1 History of discovery of the low temperature phase barium metaborate (BBO)——an excel-lent new-type ultraviolet radiation frequency-doubling crystalline materialTHE first laser excitation in 1960 with ruby (α-Al<sub>2</sub>O<sub>3</sub>: Cr) as a laser crystal and the first dou-bling of frequency (347. 15 nm) in 1961 by irradiating quartz crystal (α-SiO<sub>2</sub>) with a 694. 3nm laser beam have laid the basis for the study of laser and nonlinear optical (NLO) crystals,