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
The gas phase reactions of metal plasma with alcohol clusters were studied by time of flight mass spectrometry （TOFMS） using laser ablation-molecular beam （LAMB） method. The significant dependence of the product c...The gas phase reactions of metal plasma with alcohol clusters were studied by time of flight mass spectrometry （TOFMS） using laser ablation-molecular beam （LAMB） method. The significant dependence of the product cluster ions on the molecular beam conditions was observed. When the plasma acted on the low density parts of the pulsed molecular beam, the metal-alcohol complexes M^＋An （M=Cu, Al, Mg, Ni and A=C2H5OH, CH3OH） were the dominant products, and the sizes of product ion clusters were smaller. While the plasma acted on the high density part of the beam, however, the main products turned to be protonated alcohol clusters H^＋An and, as the reactions of plasma with methanol were concerned, the protonated water-methanol complexes H3O^＋（CH3OH）n with a larger size （n≤12 for ethanol and n≤24 for methanol）. Similarly, as the pressure of the carrier helium gas was varied from 1 × 10^5 to 5 × 10^5 Pa, the main products were changed from M^＋An to H^＋An and the sizes of the clusters also increased. The changes in the product clusters were attributed to the different formation mechanism of the output ions, that is, the M^＋An ions came from the reaction of metal ion with alcohol clusters, while H^＋An mainly from collisional reaction of electron with alcohol clusters.展开更多
1 引言近年来,由于掺杂形态的导电聚吡咯的独特的电化学性质和有用性,这类新的化合物颇受人们的关注,但至今作为催化剂用于有机合成中尚不多见。我们做了有益的探试,经用预制的或现域的化学和电化学,催化合成出了多系列多功能的新型的...1 引言近年来,由于掺杂形态的导电聚吡咯的独特的电化学性质和有用性,这类新的化合物颇受人们的关注,但至今作为催化剂用于有机合成中尚不多见。我们做了有益的探试,经用预制的或现域的化学和电化学,催化合成出了多系列多功能的新型的分子簇配合物催化剂(简称P P MC),它们多含过渡金属—有机膦形态的高导有机聚合物,用于催化CO氢化,丙烯和庚烯氢甲酰化制甲醇、正丁醇、辛醇,获得了喜人的催化活性,可观的目的产物的收率,比传统的合成醇方法,条件大为温和和优越,颇有潜在的开发前景。并对作用的理论提出了新见解。展开更多
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.
基金Project supported by the the National Natural-Science Foundation-of China （No.20573111） and 863 Project （No. 2005AA641020）.
文摘The gas phase reactions of metal plasma with alcohol clusters were studied by time of flight mass spectrometry （TOFMS） using laser ablation-molecular beam （LAMB） method. The significant dependence of the product cluster ions on the molecular beam conditions was observed. When the plasma acted on the low density parts of the pulsed molecular beam, the metal-alcohol complexes M^＋An （M=Cu, Al, Mg, Ni and A=C2H5OH, CH3OH） were the dominant products, and the sizes of product ion clusters were smaller. While the plasma acted on the high density part of the beam, however, the main products turned to be protonated alcohol clusters H^＋An and, as the reactions of plasma with methanol were concerned, the protonated water-methanol complexes H3O^＋（CH3OH）n with a larger size （n≤12 for ethanol and n≤24 for methanol）. Similarly, as the pressure of the carrier helium gas was varied from 1 × 10^5 to 5 × 10^5 Pa, the main products were changed from M^＋An to H^＋An and the sizes of the clusters also increased. The changes in the product clusters were attributed to the different formation mechanism of the output ions, that is, the M^＋An ions came from the reaction of metal ion with alcohol clusters, while H^＋An mainly from collisional reaction of electron with alcohol clusters.
文摘1 引言近年来,由于掺杂形态的导电聚吡咯的独特的电化学性质和有用性,这类新的化合物颇受人们的关注,但至今作为催化剂用于有机合成中尚不多见。我们做了有益的探试,经用预制的或现域的化学和电化学,催化合成出了多系列多功能的新型的分子簇配合物催化剂(简称P P MC),它们多含过渡金属—有机膦形态的高导有机聚合物,用于催化CO氢化,丙烯和庚烯氢甲酰化制甲醇、正丁醇、辛醇,获得了喜人的催化活性,可观的目的产物的收率,比传统的合成醇方法,条件大为温和和优越,颇有潜在的开发前景。并对作用的理论提出了新见解。
