气相催化硼加氢

T. Matsuda, Jinichi Ogawa, H. Kawashima, Motomu Ojima
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引用次数: 1

摘要

提出了一种新的烯烃气相催化硼化反应。研究了pd -碳催化剂在30 ~ 50℃条件下二硼烷与乙烯或丙烯反应的动力学。反应的初始速率ri用ri=kp1/2BPO表示,其中PB和PO分别为二硼烷和乙烯或丙烯的初始分压,k为速率常数。乙烯和丙烯的活化能分别为6和1.5kcal/mol。这些活化能比文献中发现的非催化硼氢化反应的活化能小得多。从烯烃对催化剂上解离的二硼烷的攻击这一速度决定步骤来解释反应机理。通过对二硼烷、乙烯和丙烯的吸附进一步证实了反应机理。
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Catalytic Hydroboration in Gas Phase
A new catalytic hydroboration of olefins in the gas phase has been proposed. The kinetics of the reaction of diborane with ethylene or propylene in the presence of a Pd-carbon catalyst was investigated at 30°C to 50°C The initial rate of the reaction, ri, was expressed by ri=kp1/2BPO, where PB and PO denote the initial partial pressures of diborane and ethylene or propylene, respectively, and k the rate constant. The activation energy was 6 and 1.5kcal/mol for ethylene and propylene, respectively. These activation energies were much smaller than those for noncatalytic hydroboration found in literature. The reaction mechanism was interpreted in terms of the rate-determining step which is the attack of the olefin on the dissociated diborane on the catalyst. The reaction mechanism was further confirmed by the adsorptions of diborane, ethylene and propylene.
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