A novel dimeric complex [Ru3 (μ3-O)(μ-CH3COO)(CO)]2(μ-dppf)(μ-odppf)(dppf = 1, 1'-bis(diphenylphosphio)ferrocene, odppf = 1, 1'-bis(oxodiphenylphosphoranyl)ferrocene) (1) of oxo-centered triruthenium-aecta...A novel dimeric complex [Ru3 (μ3-O)(μ-CH3COO)(CO)]2(μ-dppf)(μ-odppf)(dppf = 1, 1'-bis(diphenylphosphio)ferrocene, odppf = 1, 1'-bis(oxodiphenylphosphoranyl)ferrocene) (1) of oxo-centered triruthenium-aectate cluster units was synthesized and characterized by X-ray crystallography. Compound 1 exhibits a cyclic structure formed by linkages of two triruthenium cluster units Ru3 (μ3-O)(μ-CH3COO)6(CO) through dppf and odppf ligands, respectively. The diameter of the molecular loop is ca. 1.0 nm.展开更多
A (μ-oxo)tetraruthenium cluster showed high catalytic activity for a simple and practical aerobic oxidation of alcohols to aldehydes and ketones under 1 atm of O2 or air. After the reaction, this cluster catalyst was...A (μ-oxo)tetraruthenium cluster showed high catalytic activity for a simple and practical aerobic oxidation of alcohols to aldehydes and ketones under 1 atm of O2 or air. After the reaction, this cluster catalyst was re- covered from the reaction mixture, and we believe that this (μ-oxo)tetraruthenium cluster acts as an active catalytic species throughout the reaction.展开更多
Recently, metal clusters supported on some solids which simultaneously exhibit many excellent properties of both metal clusters and supports have been intensively studled. Such surface organometallic chemistry, which ...Recently, metal clusters supported on some solids which simultaneously exhibit many excellent properties of both metal clusters and supports have been intensively studled. Such surface organometallic chemistry, which concerns the synthesis, structure, reactivity and catalytic activity of surface-supported organometallfc compounds is a new展开更多
Hexanuclear ruthenium cluster compound Ru<sub>6</sub>C （CO）<sub>17</sub> has interesting activity in the gase-phase. The ion-molecular reaction of Ru<sub>6</sub>C （CO）<sub>...Hexanuclear ruthenium cluster compound Ru<sub>6</sub>C （CO）<sub>17</sub> has interesting activity in the gase-phase. The ion-molecular reaction of Ru<sub>6</sub>C （CO）<sub>17</sub> with triphcnylphosphine was investigated by EI-MS. The experimental results showed that Ru<sub>6</sub>C （CO）<sub>17</sub> could undergo the ligand substitution by PPh<sub>2</sub> or PPh<sub>3</sub> to initially yield monosubstituted product [Ru<sub>6</sub>C（CO）<sub>16</sub>PPh<sub>2</sub>]<sup>+</sup> or [Ru<sub>6</sub>C （CO）<sub>16</sub>PPh<sub>3</sub>]<sup>+</sup>.展开更多
Ruthenium(Ru)is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction(ORR),in virtue of its high catalytic selectivity and relatively low price.In this work,a series o...Ruthenium(Ru)is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction(ORR),in virtue of its high catalytic selectivity and relatively low price.In this work,a series of well-dispersed nitrogen-coordinated Ru-clusters on carbon black(Ru_(x)N_(y)/C)were prepared by pyrolyzing different Ru-containing sandwich compounds as the Ru sources.The higher thermal stability of these complexed sandwich precursors(bis(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)monomer,dichloro(p-cymene)Ru(II)dimer,and chloro(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)tetramer)affords the control of coordinated state for the resulting Ru-clusters,in comparison of that derived from ruthenium chlorides.After the pyrolysis treatment,the Ru coordinated state in Ru_(x)N_(y)/C,with the Ru–N and Ru–Ru bonds,still showed the structural inheritance from the Ru(II)monomer,dimer,and tetramer,but using ruthenium chlorides as the Ru source resulted in the nanoscale Ru agglomerations.The ORR testing exhibited that the Ru_(x)N_(y)/C sample derived from the Ru(II)tetramer(Ru_(x)N_(y)/C-T)presents the higher catalytic activity than the other obtained samples in either alkaline or acidic electrolytes.Even in the acidic electrolyte,Ru_(x)N_(y)/C-T shows the comparable ORR activity to that of Pt/C catalysts,and it shows the superior tolerance against methanol and CO.The X-ray absorption spectroscopy and density functional theory calculations demonstrate that these tetra-nuclear Ru-clusters could be the most active site due to their broadened d-orbital bands and lower energy d-band center than those of other subnano species and nanocrystals,and their favorable Yeager-type adsorption of O_(2)-molecules is also contributed to promoting O–O bond cleavage and accelerating the ORR process.展开更多
The reaction of Ru3(CO)12 with P(NEt2)2Cl, yields two trinuclear ruthenium carbonyl clusters: HRu3(CO)9[ μ3-η2-P(NEt2)2]2 Ⅰ (known) and a novel Ru3(CO)7( μ-Cl)2[ μ-P(NEt2)2]2 Ⅱ. During the reaction, the ligand p...The reaction of Ru3(CO)12 with P(NEt2)2Cl, yields two trinuclear ruthenium carbonyl clusters: HRu3(CO)9[ μ3-η2-P(NEt2)2]2 Ⅰ (known) and a novel Ru3(CO)7( μ-Cl)2[ μ-P(NEt2)2]2 Ⅱ. During the reaction, the ligand precursor was cleaved in its P-Cl bond to give the fragments Cl and P(NEt2)2, and then coordinated to the ruthenium atoms to form the clusters as listed above. The crystal structure of cluster Ⅱ has been determined by X-ray diffraction technique. The crystal belongs to monoclinic with space group P21 / c. The unit cell parameters are as follows: a=1.287 9(6) nm, b=1.653 9(8) nm, c=1.643 6(8) nm, β=95.786(7)°, V=3.483(3) nm3, Dc=1.756 g·cm-3, Z=4. The cluster has a closed triangle Ru3 framework. Two Ru-Ru bonds are supported by μ-P(NEt2)2, the other one is connected by double Cl bridging. The valence electrons of the cluster are 50e. CCDC: 231979.展开更多
基金This work was supported financially by the NNSF of China(No.20171044,20273074 and 20391001)NSF of Fujian Province(E03 10029).
文摘A novel dimeric complex [Ru3 (μ3-O)(μ-CH3COO)(CO)]2(μ-dppf)(μ-odppf)(dppf = 1, 1'-bis(diphenylphosphio)ferrocene, odppf = 1, 1'-bis(oxodiphenylphosphoranyl)ferrocene) (1) of oxo-centered triruthenium-aectate cluster units was synthesized and characterized by X-ray crystallography. Compound 1 exhibits a cyclic structure formed by linkages of two triruthenium cluster units Ru3 (μ3-O)(μ-CH3COO)6(CO) through dppf and odppf ligands, respectively. The diameter of the molecular loop is ca. 1.0 nm.
文摘A (μ-oxo)tetraruthenium cluster showed high catalytic activity for a simple and practical aerobic oxidation of alcohols to aldehydes and ketones under 1 atm of O2 or air. After the reaction, this cluster catalyst was re- covered from the reaction mixture, and we believe that this (μ-oxo)tetraruthenium cluster acts as an active catalytic species throughout the reaction.
文摘Recently, metal clusters supported on some solids which simultaneously exhibit many excellent properties of both metal clusters and supports have been intensively studled. Such surface organometallic chemistry, which concerns the synthesis, structure, reactivity and catalytic activity of surface-supported organometallfc compounds is a new
基金This work was supported by Fujian Natural Science Found
文摘Hexanuclear ruthenium cluster compound Ru<sub>6</sub>C （CO）<sub>17</sub> has interesting activity in the gase-phase. The ion-molecular reaction of Ru<sub>6</sub>C （CO）<sub>17</sub> with triphcnylphosphine was investigated by EI-MS. The experimental results showed that Ru<sub>6</sub>C （CO）<sub>17</sub> could undergo the ligand substitution by PPh<sub>2</sub> or PPh<sub>3</sub> to initially yield monosubstituted product [Ru<sub>6</sub>C（CO）<sub>16</sub>PPh<sub>2</sub>]<sup>+</sup> or [Ru<sub>6</sub>C （CO）<sub>16</sub>PPh<sub>3</sub>]<sup>+</sup>.
基金supported by the National Key Research and Development Program of China(No.2022YFE0110400)the National Natural Science Foundation of China(Nos.52122207,52173245,52130206,U20A20337,and 52221006)the Fundamental Research Funds for the Central Universities(No.CLYY2022).
文摘Ruthenium(Ru)is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction(ORR),in virtue of its high catalytic selectivity and relatively low price.In this work,a series of well-dispersed nitrogen-coordinated Ru-clusters on carbon black(Ru_(x)N_(y)/C)were prepared by pyrolyzing different Ru-containing sandwich compounds as the Ru sources.The higher thermal stability of these complexed sandwich precursors(bis(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)monomer,dichloro(p-cymene)Ru(II)dimer,and chloro(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)tetramer)affords the control of coordinated state for the resulting Ru-clusters,in comparison of that derived from ruthenium chlorides.After the pyrolysis treatment,the Ru coordinated state in Ru_(x)N_(y)/C,with the Ru–N and Ru–Ru bonds,still showed the structural inheritance from the Ru(II)monomer,dimer,and tetramer,but using ruthenium chlorides as the Ru source resulted in the nanoscale Ru agglomerations.The ORR testing exhibited that the Ru_(x)N_(y)/C sample derived from the Ru(II)tetramer(Ru_(x)N_(y)/C-T)presents the higher catalytic activity than the other obtained samples in either alkaline or acidic electrolytes.Even in the acidic electrolyte,Ru_(x)N_(y)/C-T shows the comparable ORR activity to that of Pt/C catalysts,and it shows the superior tolerance against methanol and CO.The X-ray absorption spectroscopy and density functional theory calculations demonstrate that these tetra-nuclear Ru-clusters could be the most active site due to their broadened d-orbital bands and lower energy d-band center than those of other subnano species and nanocrystals,and their favorable Yeager-type adsorption of O_(2)-molecules is also contributed to promoting O–O bond cleavage and accelerating the ORR process.
文摘The reaction of Ru3(CO)12 with P(NEt2)2Cl, yields two trinuclear ruthenium carbonyl clusters: HRu3(CO)9[ μ3-η2-P(NEt2)2]2 Ⅰ (known) and a novel Ru3(CO)7( μ-Cl)2[ μ-P(NEt2)2]2 Ⅱ. During the reaction, the ligand precursor was cleaved in its P-Cl bond to give the fragments Cl and P(NEt2)2, and then coordinated to the ruthenium atoms to form the clusters as listed above. The crystal structure of cluster Ⅱ has been determined by X-ray diffraction technique. The crystal belongs to monoclinic with space group P21 / c. The unit cell parameters are as follows: a=1.287 9(6) nm, b=1.653 9(8) nm, c=1.643 6(8) nm, β=95.786(7)°, V=3.483(3) nm3, Dc=1.756 g·cm-3, Z=4. The cluster has a closed triangle Ru3 framework. Two Ru-Ru bonds are supported by μ-P(NEt2)2, the other one is connected by double Cl bridging. The valence electrons of the cluster are 50e. CCDC: 231979.
