烯(火圣)醛化和羰化的新催化剂

New Catalyst for Hydroformylation and Carbonylation of Olefins

研究了钌簇合物Ru1（CO）12,H4Ru4（CO）12[PPN][HRu1（CO）11],[PPN][H3Ru4（CO）12]（PPN=[（Ph2P）2N]）和Ru2（CO）2.（dpm）3（dpm=ph2p-m-C4H4SO3Na）等摧化乙烯的醛化,报道了可溶性的Ru3（CO）2（dpm）在水溶液中催化丙烯和乙烯的醛化、羰化的性能,在反应温度120℃,反应气体总压为2.7～5.OMPa的条件下,丙烯和乙烯的醛化活性随反应温度、催化剂浓度和气体分压（CO/H2=1:1）的提高而提高,温度的变化对活性的影响最明显,溶液的酸碱性也影响催化活性,中性对反应最有利,添加无机和有机卤化物显著地影响乙烯的醛化活性和产物分布,乙烯羰化生成二乙基酮的选择性高达52.7％,其反应前后的钉簇合物催化剂分别经IR和XPS表征,讨论了可能的催化活性物种。

Ru3(CO)12,H4Ru4(CO)12,[PPN][HRu3(CO)11][PPN][H3Ru4(CO)12] and Ru3 (CO)β(dpm)3(dpm-ph2p-m-C6H4SO3Na) were used as catalysts to hydroforroylate ethylene. Water-soluble and air-stable Ru3(CO)9(dpm)3 was firstly investigated as a new catalyst for hydroformylation of propylene and ethylene, Reppe reaction and carbonylation of ethylene with CO/H2O or CO/H2 in water. For propylene hydroformylation under milder reaction conditions, catalytic activity was found to increase with increasing of reaction temperature,catalyst concentration ofr partial pressures of the gaseous reagents(CO/H2= 1) , and the highest n/i ratio of 15. 9/1 was obtained. In the case of ethylene, Ru3(CO)9(dpm)3 was found to catalyze Reppe reaction involving C2H4/CO in neutral water. For ethylene hydroformylation, addition of various halide promoters greatly inhances the catalytic activity and leads to selective formation of diethyl ketone. The catalyst was also characterized before and after the reaction by IR and XPS and the results were discussed as related to the possible catalytic species.