The complex containing ferroceneyl, Cd(dppf)I2(dppf=1,1 bis(diphenylphosphino) ferrocene), was synthesized and characterized by IR, Uv vis DRIS spectrum and X ray diffraction. The crystal belongs to monoclinic, space ...The complex containing ferroceneyl, Cd(dppf)I2(dppf=1,1 bis(diphenylphosphino) ferrocene), was synthesized and characterized by IR, Uv vis DRIS spectrum and X ray diffraction. The crystal belongs to monoclinic, space group C2/c, a=37.439(3)?, b=10.2472(6)?, c=18.719(1)?, β=110.4715(16)°, V=6727.8(8)?3, Z=8, Dc=1.818g·cm-3, F(000)=3536, μ=3.015mm-1, R=0.0308, wR=0.0692. dppf coordinates to Cd? as bidentate ligand, and the coordination environment of Cd? is a distorted tetrahedron. The electronic structures of Cd(dppf)I2 and Cd(dppf)Br2 are discussed by quantum chemistry calculation.展开更多
By the reaction of bidentate ligand 1,1'-bis(diphenylphosphino)-ferrocene (dppf) with MoCl_4(CH_3CN)_2, a novel bonding type complex (MoCl_4)2_· (dppf) was synthesized and characterized by elemental analyses,...By the reaction of bidentate ligand 1,1'-bis(diphenylphosphino)-ferrocene (dppf) with MoCl_4(CH_3CN)_2, a novel bonding type complex (MoCl_4)2_· (dppf) was synthesized and characterized by elemental analyses, ^(31)p-NMR, IR and electronic spectra, TG and ICP-AES. Structure of the title complex was proposed.展开更多
A large surface-to-volume ratio is one of the most intriguing characteristics of nanoclusters,which endows the nanoclusters with novel properties and applications.In this work,surface engineering with a functional DPP...A large surface-to-volume ratio is one of the most intriguing characteristics of nanoclusters,which endows the nanoclusters with novel properties and applications.In this work,surface engineering with a functional DPPF ligand and Cd atom is employed on a Au_(38)nanocluster to obtain a Au–Cd alloy nanocluster,that is,Au_(27)Cd_(1)(SAdm)_(14)(DPPF)Cl(Au_(27)Cd1 in short,DPPF=1,1’-bis(diphenylphosphino)ferrocene,HSAdm=1-adamantanethiol).Various characterization techniques are used to characterize the precise formulation and atomic structure of the Au_(27)Cd1 nanocluster.To demonstrate the influence of surface engineering on the properties of nanoclusters,the difference in optical,electrochemical and electrocatalytic activities in the oxygen reduction reaction(ORR)between Au_(38)and Au_(27)Cd1,as well as the stability of Au_(27)Cd1,is explored.The results indicate the importance of surface engineering,that is,the introduction of functional ligands and surface doping of Cd atoms contribute to the enhancement of catalytic activity.This work sheds light on the surface engineering of nanoclusters and provides a new perspective for the performance optimization of nanoclusters.展开更多
Two 1,1′-azaphospha substituted dppf-analogues Fc′(NMe_(2))(PPh_(2))(Ph=C_(6)H_(5),Fc′=1,1′-ferrocenediyl,3a)and Fc′(NMe_(2))(PMes_(2))(Mes=_(2),4,6-Me_(3)C_(6)H_(2),3b)have been prepared,via reductive amination,...Two 1,1′-azaphospha substituted dppf-analogues Fc′(NMe_(2))(PPh_(2))(Ph=C_(6)H_(5),Fc′=1,1′-ferrocenediyl,3a)and Fc′(NMe_(2))(PMes_(2))(Mes=_(2),4,6-Me_(3)C_(6)H_(2),3b)have been prepared,via reductive amination,followed by salt-metathesis(of 2),starting from 1,1′-azabromoferrocene 1.Their donor properties have been explored using heteronuclear NMR spectroscopy based on their^(1)JP-Se coupling,and the formation of PdCl_(2)-complexes in comparison to a set of related dppf analogs with gradual steric variation,such as Fc′(PMes_(2))(PPh_(2))(5)and Fc′(PMes_(2))(PtBu_(2))(6).Chloride abstraction from these complexes,namely Fc′(PMes_(2))(PPh_(2))·PdCl_(2)(7),Fc′(PMes_(2))(PtBu_(2))·PdCl_(2)(8),and[Fc′(NMe_(2))(PPh_(2))]_(2)·PdCl_(2)(9)using AgSbF_(6)produced the corresponding cationic Pd(II)complexes[Fc′(PMes_(2))(PtBu_(2))·PdCl][SbF_(6)](10),[Fc′(PPh_(2))(NMe_(2))·PdCl][SbF_(6)]_(2)(11)and[Fc′(PPh_(2))(NMe_(2))·Pd(PPh_(2)C_(5)H_(5))][SbF_(6)]_(2)(1_(2))featuring Fe→Pd interactions.Variation of the counter anion by coordination of 3a to a chloride-free Pd(II)source furnished[Fc′(PPh_(2))(NMe_(2))·Pd(PPh_(3))][BF_(4)]_(2)(13),[Fc′(PPh_(2))(NMe_(2))·Pd(PPh_(2))Fc′(NMe_(2))][BF_(4)]_(2)(14),and[Fc′(PPh_(2))(NMe_(2))·PdP(p-OMe-C_(6)H_(4))_(3)][BF_(4)]_(2)(15)with similar Fe→Pd interactions.Comparison with previously reported diphospha-and azaphospha-counterparts,revealed that 10 and 11 display the shortest and 15 the longest Fe-Pd bond,within their ligand scaffold congeners.DFT calculations performed on compounds 10-15 were further able to verify their intrinsic structural features and trends and shed light on the nature of the Fe→Pd bonding interactions which are furthermore consistent with CV measurements.展开更多
针对传统动态概率潮流(dynamic probability power flow,DPPF)计算结果存在的保守性问题,提出一种计及风速预测误差时空相关性的DPPF计算方法。首先,采用自相关系数平稳过程描述输入变量的预测误差过程,利用非参数核密度估计直接根据预...针对传统动态概率潮流(dynamic probability power flow,DPPF)计算结果存在的保守性问题,提出一种计及风速预测误差时空相关性的DPPF计算方法。首先,采用自相关系数平稳过程描述输入变量的预测误差过程,利用非参数核密度估计直接根据预测误差历史数据拟合得到预测误差分布;其次,基于等概率变换理论和Nataf变换技术得到具有时空相关性的误差样本。最后,通过基于拉丁超立方采样的蒙特卡罗模拟法进行DPPF计算,得到节点电压幅值和支路潮流的数字特征和动态概率分布。采用IEEE 14节点和IEEE 118节点系统进行仿真,验证了算法准确性和效率。展开更多
The atom-level manipulation of atomically precise metal nanoclusters(NCs)has attracted considerable attention due to its potential for facilitating the elucidation of structure-property relationships.Herein,we report ...The atom-level manipulation of atomically precise metal nanoclusters(NCs)has attracted considerable attention due to its potential for facilitating the elucidation of structure-property relationships.Herein,we report two atomically precise gold NCs,[Au_(9)(DPPF)_(4)]Cl_(3)(DPPF=bis(diphenylphosphino)ferrocene)(Au_(9))and[Au_(8)(DPPF)_(4)]Cl_(2)(Au_(8)),identified by single-crystal X-ray diffraction(SCXRD)and electrospray ionization mass spectrometry(ESI-MS).SCXRD analysis revealed that the two gold NCs contain a similar Au_(8)unit enclosed by a tetrahedral framework consisting of four DPPF ligands,and the only difference is the addition of a gold atom on the kernel surface of the Au_(9)NC,which can be resected to form the Au_(8)NC.This represents the achievement of precise atomic“tailoring”of the surface of a kernel of a gold NC without altering the other parts of the structure.Notably,the two NCs allow for the identification of free valence electrons(6e).A further investigation into their electronic structures and electrocatalytic CO_(2)reduction reaction activity was performed to explore the functionality of such minimal kernel tailoring at the atomic level.This study not only enriches the family of diphosphine-protected small-sized gold NCs but also realizes the atomic-level tailoring of specific sites on a nanoparticle.展开更多
A facile method for the carbonylative cycliza- tion of o-bromobenzoic acid with primary amine using Pd（OAC）2 as a metal precursor and 1, l′-bis（diphenylpho- sphino）ferrocene （dppf） as a ligand has been develope...A facile method for the carbonylative cycliza- tion of o-bromobenzoic acid with primary amine using Pd（OAC）2 as a metal precursor and 1, l′-bis（diphenylpho- sphino）ferrocene （dppf） as a ligand has been developed. The effect of various reaction parameters such as ligand, solvent, base, time and temperature on this cyclization was studied. The optimized protocol was used for a wide variety of substituted aryl amines with different steric and electronic properties, affording the corresponding isoindoline-l,3-diones in good to excellent yields under atmospheric pressure of carbon monoxide at 100℃ within 10h using 1,4-diazabicyclo[2.2.2]octane （DABCO） as a base. The reaction system finds attractive alternative to the conventional multistep synthetic process and thus repre- sents an effective utilization of carbonylative protocol for synthesis of valuable chemicals.展开更多
文摘The complex containing ferroceneyl, Cd(dppf)I2(dppf=1,1 bis(diphenylphosphino) ferrocene), was synthesized and characterized by IR, Uv vis DRIS spectrum and X ray diffraction. The crystal belongs to monoclinic, space group C2/c, a=37.439(3)?, b=10.2472(6)?, c=18.719(1)?, β=110.4715(16)°, V=6727.8(8)?3, Z=8, Dc=1.818g·cm-3, F(000)=3536, μ=3.015mm-1, R=0.0308, wR=0.0692. dppf coordinates to Cd? as bidentate ligand, and the coordination environment of Cd? is a distorted tetrahedron. The electronic structures of Cd(dppf)I2 and Cd(dppf)Br2 are discussed by quantum chemistry calculation.
文摘By the reaction of bidentate ligand 1,1'-bis(diphenylphosphino)-ferrocene (dppf) with MoCl_4(CH_3CN)_2, a novel bonding type complex (MoCl_4)2_· (dppf) was synthesized and characterized by elemental analyses, ^(31)p-NMR, IR and electronic spectra, TG and ICP-AES. Structure of the title complex was proposed.
基金the National Natural Science Foundation of China(21631001,21871001 and 22001003)the Ministry of Education,and the University Synergy Innovation Program of Anhui Province(GXXT-2020-053).
文摘A large surface-to-volume ratio is one of the most intriguing characteristics of nanoclusters,which endows the nanoclusters with novel properties and applications.In this work,surface engineering with a functional DPPF ligand and Cd atom is employed on a Au_(38)nanocluster to obtain a Au–Cd alloy nanocluster,that is,Au_(27)Cd_(1)(SAdm)_(14)(DPPF)Cl(Au_(27)Cd1 in short,DPPF=1,1’-bis(diphenylphosphino)ferrocene,HSAdm=1-adamantanethiol).Various characterization techniques are used to characterize the precise formulation and atomic structure of the Au_(27)Cd1 nanocluster.To demonstrate the influence of surface engineering on the properties of nanoclusters,the difference in optical,electrochemical and electrocatalytic activities in the oxygen reduction reaction(ORR)between Au_(38)and Au_(27)Cd1,as well as the stability of Au_(27)Cd1,is explored.The results indicate the importance of surface engineering,that is,the introduction of functional ligands and surface doping of Cd atoms contribute to the enhancement of catalytic activity.This work sheds light on the surface engineering of nanoclusters and provides a new perspective for the performance optimization of nanoclusters.
基金financial support.Z.K.is grateful for the general support of János Bolyai Research Scholarship,Project UNKP-22-5-BME-298 and TKP2021-EGA-02 provided by the Ministry of Innovation and Technology of Hungary.
文摘Two 1,1′-azaphospha substituted dppf-analogues Fc′(NMe_(2))(PPh_(2))(Ph=C_(6)H_(5),Fc′=1,1′-ferrocenediyl,3a)and Fc′(NMe_(2))(PMes_(2))(Mes=_(2),4,6-Me_(3)C_(6)H_(2),3b)have been prepared,via reductive amination,followed by salt-metathesis(of 2),starting from 1,1′-azabromoferrocene 1.Their donor properties have been explored using heteronuclear NMR spectroscopy based on their^(1)JP-Se coupling,and the formation of PdCl_(2)-complexes in comparison to a set of related dppf analogs with gradual steric variation,such as Fc′(PMes_(2))(PPh_(2))(5)and Fc′(PMes_(2))(PtBu_(2))(6).Chloride abstraction from these complexes,namely Fc′(PMes_(2))(PPh_(2))·PdCl_(2)(7),Fc′(PMes_(2))(PtBu_(2))·PdCl_(2)(8),and[Fc′(NMe_(2))(PPh_(2))]_(2)·PdCl_(2)(9)using AgSbF_(6)produced the corresponding cationic Pd(II)complexes[Fc′(PMes_(2))(PtBu_(2))·PdCl][SbF_(6)](10),[Fc′(PPh_(2))(NMe_(2))·PdCl][SbF_(6)]_(2)(11)and[Fc′(PPh_(2))(NMe_(2))·Pd(PPh_(2)C_(5)H_(5))][SbF_(6)]_(2)(1_(2))featuring Fe→Pd interactions.Variation of the counter anion by coordination of 3a to a chloride-free Pd(II)source furnished[Fc′(PPh_(2))(NMe_(2))·Pd(PPh_(3))][BF_(4)]_(2)(13),[Fc′(PPh_(2))(NMe_(2))·Pd(PPh_(2))Fc′(NMe_(2))][BF_(4)]_(2)(14),and[Fc′(PPh_(2))(NMe_(2))·PdP(p-OMe-C_(6)H_(4))_(3)][BF_(4)]_(2)(15)with similar Fe→Pd interactions.Comparison with previously reported diphospha-and azaphospha-counterparts,revealed that 10 and 11 display the shortest and 15 the longest Fe-Pd bond,within their ligand scaffold congeners.DFT calculations performed on compounds 10-15 were further able to verify their intrinsic structural features and trends and shed light on the nature of the Fe→Pd bonding interactions which are furthermore consistent with CV measurements.
基金supported by the National Natural Science Foundation of China(21672105,21725204,91753124)Natural Science Foundation of Tianjin,China(17JCYBJC19700,18JCZDJC32800)~~
文摘针对传统动态概率潮流(dynamic probability power flow,DPPF)计算结果存在的保守性问题,提出一种计及风速预测误差时空相关性的DPPF计算方法。首先,采用自相关系数平稳过程描述输入变量的预测误差过程,利用非参数核密度估计直接根据预测误差历史数据拟合得到预测误差分布;其次,基于等概率变换理论和Nataf变换技术得到具有时空相关性的误差样本。最后,通过基于拉丁超立方采样的蒙特卡罗模拟法进行DPPF计算,得到节点电压幅值和支路潮流的数字特征和动态概率分布。采用IEEE 14节点和IEEE 118节点系统进行仿真,验证了算法准确性和效率。
基金supported by the National Natural Science Foundation of China(22371108,21971246,22209002)the Taishan Scholar Foundation of Shandong Province(tsqn202211242)the Natural Science Foundation of Shandong Province(ZR2024MB125,ZR2024MB007,ZR2024QB238,and ZR2020QB031).
文摘The atom-level manipulation of atomically precise metal nanoclusters(NCs)has attracted considerable attention due to its potential for facilitating the elucidation of structure-property relationships.Herein,we report two atomically precise gold NCs,[Au_(9)(DPPF)_(4)]Cl_(3)(DPPF=bis(diphenylphosphino)ferrocene)(Au_(9))and[Au_(8)(DPPF)_(4)]Cl_(2)(Au_(8)),identified by single-crystal X-ray diffraction(SCXRD)and electrospray ionization mass spectrometry(ESI-MS).SCXRD analysis revealed that the two gold NCs contain a similar Au_(8)unit enclosed by a tetrahedral framework consisting of four DPPF ligands,and the only difference is the addition of a gold atom on the kernel surface of the Au_(9)NC,which can be resected to form the Au_(8)NC.This represents the achievement of precise atomic“tailoring”of the surface of a kernel of a gold NC without altering the other parts of the structure.Notably,the two NCs allow for the identification of free valence electrons(6e).A further investigation into their electronic structures and electrocatalytic CO_(2)reduction reaction activity was performed to explore the functionality of such minimal kernel tailoring at the atomic level.This study not only enriches the family of diphosphine-protected small-sized gold NCs but also realizes the atomic-level tailoring of specific sites on a nanoparticle.
文摘A facile method for the carbonylative cycliza- tion of o-bromobenzoic acid with primary amine using Pd（OAC）2 as a metal precursor and 1, l′-bis（diphenylpho- sphino）ferrocene （dppf） as a ligand has been developed. The effect of various reaction parameters such as ligand, solvent, base, time and temperature on this cyclization was studied. The optimized protocol was used for a wide variety of substituted aryl amines with different steric and electronic properties, affording the corresponding isoindoline-l,3-diones in good to excellent yields under atmospheric pressure of carbon monoxide at 100℃ within 10h using 1,4-diazabicyclo[2.2.2]octane （DABCO） as a base. The reaction system finds attractive alternative to the conventional multistep synthetic process and thus repre- sents an effective utilization of carbonylative protocol for synthesis of valuable chemicals.
