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
NaY zeolite entrapped Ru3(CO)12 cluster has been synthesized from RuCl3 ion-exchanged NaY, which is well characterized by IR and Raman spectroscopies and CO chemisorp-tion. When the Ru3+/NaY sample is heated from 298 ...NaY zeolite entrapped Ru3(CO)12 cluster has been synthesized from RuCl3 ion-exchanged NaY, which is well characterized by IR and Raman spectroscopies and CO chemisorp-tion. When the Ru3+/NaY sample is heated from 298 K to 393 K for 25 h and for 10 h at 393 K, the sample colour changes from dark to brown-yellow. The in situ infrared spectrum exhibits absorption bands at 2130, 2064, 2040, 2017, 1990, 1953 and 1925 cm-1. The bands at 2130 cm-1 arises from the Runm+(CO)l m =1-3;n = 1 - 3; l = 1-12). The bands at 2064, 2040, 2017 and 1990 cm-1 are proposed to be associated with the Ru3(CO)12/NaY, which are close to Ru3(CO)12 crystalline. Furthermore, the Raman results provide bands at 150 and 185 cm-1, which can be attributed to Ru-Ru bonds of the sample as in the case of Ru3(CO)12 crystalline, for which the A1' Ru-Ru stretching mode is assigned to 185 cm-1 and E1' Ru-Ru stretching mode is assigned to a band at 150 cm-1, respectively. CO chemisorption of [Ru3]/NaY gives a CO/Ru ratio of 3.85, which is similar to the stoichiometry of Ru3(CO)12.展开更多
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.
基金Project supported by the National Natural Science Foundation of China for Young Scientists and the Excellent Junior Faculty Foundation of the State Education Commission.
文摘NaY zeolite entrapped Ru3(CO)12 cluster has been synthesized from RuCl3 ion-exchanged NaY, which is well characterized by IR and Raman spectroscopies and CO chemisorp-tion. When the Ru3+/NaY sample is heated from 298 K to 393 K for 25 h and for 10 h at 393 K, the sample colour changes from dark to brown-yellow. The in situ infrared spectrum exhibits absorption bands at 2130, 2064, 2040, 2017, 1990, 1953 and 1925 cm-1. The bands at 2130 cm-1 arises from the Runm+(CO)l m =1-3;n = 1 - 3; l = 1-12). The bands at 2064, 2040, 2017 and 1990 cm-1 are proposed to be associated with the Ru3(CO)12/NaY, which are close to Ru3(CO)12 crystalline. Furthermore, the Raman results provide bands at 150 and 185 cm-1, which can be attributed to Ru-Ru bonds of the sample as in the case of Ru3(CO)12 crystalline, for which the A1' Ru-Ru stretching mode is assigned to 185 cm-1 and E1' Ru-Ru stretching mode is assigned to a band at 150 cm-1, respectively. CO chemisorption of [Ru3]/NaY gives a CO/Ru ratio of 3.85, which is similar to the stoichiometry of Ru3(CO)12.
