CLUSTER VERSUS NONCLUSTER CATALYSIS IN OLEFIN THERMAL-ISOMERIZATION AND HYDROSILYLATION IN THE PRESENCE OF RU3(CO)12
CLUSTER VERSUS NONCLUSTER CATALYSIS IN OLEFIN THERMAL-ISOMERIZATION AND HYDROSILYLATION IN THE PRESENCE OF RU3(CO)12
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DOI：
10.1016/0022-328x(93)83186-y
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发表时间：
1993-06-15
影响因子：
2.3
通讯作者：
JONDI, W
中科院分区：
文献类型：
--
作者：
HILAL, HS;KHALAF, S;JONDI, W
钌簇合物Ru 3（CO）12（1）作为催化剂前体，在50-75 ℃的温度下，在二氧六环和苯的混合物中，用于1-辛烯与（Eto）3SiH的热反应。在70 ℃或更高温度下，观察到烯烃异构化和氢化硅烷化反应;鉴定了产物反式-2-辛烯和C5 H11 CH 2CH 2CH 2Si（OEt）3（2）。这些反应伴随着一个涉及氢气生成的副反应。2和H-2的出现率之和等于（EtO）3SiH的消失率。在不存在（EtO）3SiH的情况下，未观察到显著的异构化。异构化，氢化硅烷化，和H-2生产反应，分别获得750，70，和70的最大营业额数值。在60 ℃或更低温度下，没有观察到氢化硅烷化或氢产生，并且唯一的产物是反式-2-辛烯。未观察到（EtO）3SiH的可检测消失。苯乙酮也通过使用簇1作为催化剂进行硅氢化;获得的唯一产物是（Et 0）3SiOC（Ph）（H）（CH 3）。动力学研究表明，1-辛烯和苯乙酮的反应涉及一个低核度的催化活性物种。有证据表明，并发集群催化，特别是在最初的几分钟的反应。
The ruthenium cluster Ru3(CO)12 (1) has been evaluated as a catalyst precursor for the thermal reactions of 1-octene with (Eto)3SiH in a mixture of dioxane and benzene at temperatures of 50-75-degrees-C. At 70-degrees-C or higher, olefin isomerization and hydrosilylation reactions were observed; the products, trans-2-octene and C5H11CH2CH2CH2Si(OEt)3 (2) were identified. The reactions were accompanied by a side reaction that involved generation of hydrogen gas. The sum of the rates of appearance of 2 and H-2 equalled the rate of disappearance of (EtO)3SiH. No significant isomerization was observed in the absence of (EtO)3SiH. Maximum turnover number values of 750, 70, and 70 were obtained for isomerization, hydrosilylation, and H-2 production reactions, respectively. At 60-degrees-C or lower, no hydrosilylation or hydrogen production was observed, and the only product was trans-2-octene. No detectable disappearance of (EtO)3SiH was observed. Acetophenone was also hydrosilated by use of cluster 1, as catalyst; the only product obtained was (Eto)3SiOC(Ph)(H)(CH3). Kinetic studies indicated that the reactions of 1-octene and the reaction of acetophenone involved a catalytically active species of lower nuclearity. There was evidence of concurrent cluster catalysis, especially during the first few minutes of the reaction.