Water oxidation is significant in both natural and artificial photosynthesis.In nature,water oxidation occurs at the oxygen‐evolving center of photosystem II,and leads to the generation of oxygen,protons,and electron...Water oxidation is significant in both natural and artificial photosynthesis.In nature,water oxidation occurs at the oxygen‐evolving center of photosystem II,and leads to the generation of oxygen,protons,and electrons.The last two are used for fixation of carbon dioxide to give carbohydrates.In artificial processes,the coupling of water oxidation to evolve O2and water reduction to evolve H2is known as water splitting,which is an attractive method for solar energy conversion and storage.Because water oxidation is a thermodynamically uphill reaction and is kinetically slow,this reaction causes a bottleneck in large‐scale water splitting.As a consequence,the development of new and efficient water oxidation catalysts(WOCs)has attracted extensive attention.Recent efforts have identified a variety of mononuclear earth‐abundant transition‐metal complexes as active and stable molecular WOCs.This review article summarizes recent progress in research on mononuclear catalysts that are based on first‐row transition‐metal elements,namely manganese,iron,cobalt,nickel,and copper.Particular attention is paid to catalytic mechanisms and the key O?O bond formation steps.This information is critical for designing new catalysts that are highly efficient and stable.展开更多
Transition-metal-catalyzed C–H activation reaction has proven to be a powerful and efficient tool for the formation of diverse C-C and C–X bond and construction of functional complex molecules.From the viewpoint of ...Transition-metal-catalyzed C–H activation reaction has proven to be a powerful and efficient tool for the formation of diverse C-C and C–X bond and construction of functional complex molecules.From the viewpoint of sustainable chemistry,the first-row transition metals,such as Mn,Fe,Co,Ni and Cu,have been recognized as cheap,environmentally friendly and reactively effective catalysts for a number of C-H functionalization reactions.However,compared with the commonly used alkenes and alkynes in the first-row transition-metal-catalyzed C–H activations,considerable achievements have just been made by the use of structurally unique and reactively rich allenes as coupling partners in recent years.This review summarizes the recent progress of the first-row transition-metal-catalyzed C–H activations with allenes.展开更多
The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in ab...The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.展开更多
We perform the self-consistent calculations on the atomic electron affinity and ionization energy for the first-row atoms by means of our scheme. A striking feature of the present work is the variational method with t...We perform the self-consistent calculations on the atomic electron affinity and ionization energy for the first-row atoms by means of our scheme. A striking feature of the present work is the variational method with taking into account effects of the nonspherical distribution of electrons explicitly. Comparing the present results with those of the conventional spherical approximation, the systematical improvement can be found. This means that effects of the nonspherical distribution of electrons may play an essential role on the description of the atomic structures.展开更多
The enthalpy change of the complexation reactions of the first-row transitional metal chlorides including CrCl3, MnCl2, FeCl2, CoCl2, NiCl2 and CuCl2 with L--histidine in water were determined by a microcalorimeter at...The enthalpy change of the complexation reactions of the first-row transitional metal chlorides including CrCl3, MnCl2, FeCl2, CoCl2, NiCl2 and CuCl2 with L--histidine in water were determined by a microcalorimeter at 298.15—323.15 K. The standard enthalpy of formation of 32Cr(His)+(aq) and 22M(His)+(aq) (M=Mn, Fe, Co, Ni and Cu) were calculated. Based on the thermodynamic and kinetic equations of the reactions, three thermody-namic parameters (the activation enthalpy, the activation entropy, the activation free energy), the rate constants, and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) are obtained. The solid complexes of CrCl3, MnCl2, FeCl2, CoCl2, NiCl2 and CuCl2 with histidine were prepared and identified as Cr(His)2Cl3H2O, Mn(His)2Cl24H2O, Fe(His)2Cl2H2O, Co(His)2Cl2H2O, Ni(His)2Cl2H2O and Cu(His)2Cl2H2O by chemical and elemental analyses. The bonding characteristics of these complexes were char-acterized by IR as well. The results showed that, with the atomic number increasing, three thermodynamic parame-ters, GD!, HD! and SD! of the complexation reaction of these metal chlorides with L-a-histidine in water present an analogy regularity.展开更多
基金supported by Thousand Talents Program of Chinathe National Natural Science Foundation of China (21101170,21573139,and 21773146)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Research Funds of Shaanxi Normal University
文摘Water oxidation is significant in both natural and artificial photosynthesis.In nature,water oxidation occurs at the oxygen‐evolving center of photosystem II,and leads to the generation of oxygen,protons,and electrons.The last two are used for fixation of carbon dioxide to give carbohydrates.In artificial processes,the coupling of water oxidation to evolve O2and water reduction to evolve H2is known as water splitting,which is an attractive method for solar energy conversion and storage.Because water oxidation is a thermodynamically uphill reaction and is kinetically slow,this reaction causes a bottleneck in large‐scale water splitting.As a consequence,the development of new and efficient water oxidation catalysts(WOCs)has attracted extensive attention.Recent efforts have identified a variety of mononuclear earth‐abundant transition‐metal complexes as active and stable molecular WOCs.This review article summarizes recent progress in research on mononuclear catalysts that are based on first‐row transition‐metal elements,namely manganese,iron,cobalt,nickel,and copper.Particular attention is paid to catalytic mechanisms and the key O?O bond formation steps.This information is critical for designing new catalysts that are highly efficient and stable.
基金support of this work by the National Natural Science Foundation of China (No. 21502242)the State Key Laboratory of Natural and Biomimetic Drugs (No. K20150215)
文摘Transition-metal-catalyzed C–H activation reaction has proven to be a powerful and efficient tool for the formation of diverse C-C and C–X bond and construction of functional complex molecules.From the viewpoint of sustainable chemistry,the first-row transition metals,such as Mn,Fe,Co,Ni and Cu,have been recognized as cheap,environmentally friendly and reactively effective catalysts for a number of C-H functionalization reactions.However,compared with the commonly used alkenes and alkynes in the first-row transition-metal-catalyzed C–H activations,considerable achievements have just been made by the use of structurally unique and reactively rich allenes as coupling partners in recent years.This review summarizes the recent progress of the first-row transition-metal-catalyzed C–H activations with allenes.
文摘The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.
文摘We perform the self-consistent calculations on the atomic electron affinity and ionization energy for the first-row atoms by means of our scheme. A striking feature of the present work is the variational method with taking into account effects of the nonspherical distribution of electrons explicitly. Comparing the present results with those of the conventional spherical approximation, the systematical improvement can be found. This means that effects of the nonspherical distribution of electrons may play an essential role on the description of the atomic structures.
基金Projected supported by the National Natural Science Foundation of China (Nos. 299871032 and 20171036) and the National Natural Science Foun-dation of Shaanxi Province (No. FF02328).
文摘The enthalpy change of the complexation reactions of the first-row transitional metal chlorides including CrCl3, MnCl2, FeCl2, CoCl2, NiCl2 and CuCl2 with L--histidine in water were determined by a microcalorimeter at 298.15—323.15 K. The standard enthalpy of formation of 32Cr(His)+(aq) and 22M(His)+(aq) (M=Mn, Fe, Co, Ni and Cu) were calculated. Based on the thermodynamic and kinetic equations of the reactions, three thermody-namic parameters (the activation enthalpy, the activation entropy, the activation free energy), the rate constants, and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) are obtained. The solid complexes of CrCl3, MnCl2, FeCl2, CoCl2, NiCl2 and CuCl2 with histidine were prepared and identified as Cr(His)2Cl3H2O, Mn(His)2Cl24H2O, Fe(His)2Cl2H2O, Co(His)2Cl2H2O, Ni(His)2Cl2H2O and Cu(His)2Cl2H2O by chemical and elemental analyses. The bonding characteristics of these complexes were char-acterized by IR as well. The results showed that, with the atomic number increasing, three thermodynamic parame-ters, GD!, HD! and SD! of the complexation reaction of these metal chlorides with L-a-histidine in water present an analogy regularity.
