A nickel(II) complex Ni(DPBP-SAH)2·2CH3CH2OH, (DPBP-SAH=N-(1,3-diphenyl-4-benzylidene-5-pyrazolone)-salicylidene hydrazone), has been synthesized and characterized by elemental analyses, IR spectra and single cry...A nickel(II) complex Ni(DPBP-SAH)2·2CH3CH2OH, (DPBP-SAH=N-(1,3-diphenyl-4-benzylidene-5-pyrazolone)-salicylidene hydrazone), has been synthesized and characterized by elemental analyses, IR spectra and single crystal X-ray diffraction. It belongs to monoclinic, space group C2/c with a=2.737 9(4) nm, b=1.249 2(2) nm, c=1.760 8(2) nm, β=120.212(9)°, Mr=1 065.84, V=5.204(1) nm3, Z=4. The X-ray diffraction reveals that the nickel(II) ion in the title complex is in a slightly distorted octahedral arrangement of the ON donor atoms of two DPBP-SAH and two O-donor atoms in ethanol. CCDC: 249394.展开更多
A new tridentate Ni(Ⅱ) complex {Ni(H2O)3[Ph2(o-Ph-N-C7H7N)]PO}Cl2 was synthesized by the reaction of a new ligand Ph2(o-Ph-N-C7H7N)]PO with NiCl2 in C H3CH2OH. The complex was characterized by X-ray single crystal di...A new tridentate Ni(Ⅱ) complex {Ni(H2O)3[Ph2(o-Ph-N-C7H7N)]PO}Cl2 was synthesized by the reaction of a new ligand Ph2(o-Ph-N-C7H7N)]PO with NiCl2 in C H3CH2OH. The complex was characterized by X-ray single crystal diffraction. The crystal structure of the complex belongs to monoclinic space group P21/n, a=1.25 9 28(9) nm, b=1.201 24(8) nm, c=2.039 03(14) nm, V=3.016 8(4) nm-3, Z=4, and R1= 0.047 1, wR2=0.120 5. And a molecular CH2Cl2 is filled in the crystal structure. CCDC: 241832.展开更多
Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Co...Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.展开更多
文摘A nickel(II) complex Ni(DPBP-SAH)2·2CH3CH2OH, (DPBP-SAH=N-(1,3-diphenyl-4-benzylidene-5-pyrazolone)-salicylidene hydrazone), has been synthesized and characterized by elemental analyses, IR spectra and single crystal X-ray diffraction. It belongs to monoclinic, space group C2/c with a=2.737 9(4) nm, b=1.249 2(2) nm, c=1.760 8(2) nm, β=120.212(9)°, Mr=1 065.84, V=5.204(1) nm3, Z=4. The X-ray diffraction reveals that the nickel(II) ion in the title complex is in a slightly distorted octahedral arrangement of the ON donor atoms of two DPBP-SAH and two O-donor atoms in ethanol. CCDC: 249394.
文摘A new tridentate Ni(Ⅱ) complex {Ni(H2O)3[Ph2(o-Ph-N-C7H7N)]PO}Cl2 was synthesized by the reaction of a new ligand Ph2(o-Ph-N-C7H7N)]PO with NiCl2 in C H3CH2OH. The complex was characterized by X-ray single crystal diffraction. The crystal structure of the complex belongs to monoclinic space group P21/n, a=1.25 9 28(9) nm, b=1.201 24(8) nm, c=2.039 03(14) nm, V=3.016 8(4) nm-3, Z=4, and R1= 0.047 1, wR2=0.120 5. And a molecular CH2Cl2 is filled in the crystal structure. CCDC: 241832.
基金supported by the National Natural Science Foundation of China(22302115,22072079)the Fundamental Research Program of Shanxi Province(202303021221056).
文摘Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.
