The catalytic activity of anionic ruthenium complexes toward the transformation of bio-ethanol to 1-butanol and higher alcohols is found to be dependent on the imidazolium counterion. After the identification of a parallel reaction involving the catalyst in hydrogen evolution, conversion and selectivity are impressively boosted by the addition of p-benzoquinones as co-catalysts. The catalytic system avoids the side reaction and led to highly competitive conversions up to 88% (0.2 % mol ruthenium catalyst loading, 1.5 % mol benzoquinone loading). Butanol and higher alcohols are produced in yields up to 85% (overall selectivity 97%) as a mixture of valuable alcohols for advanced biofuel and lubricants applications. The catalytic system can be recycled and the reaction shows comparable efficiency on a real matrix (alcohol from wine production chain wastes) even in the presence of significant amounts of water, thus closing a hypothetic economic circle. A reaction mechanism is proposed for the most promising ruthenium complex working in cooperation with the most efficient co-catalyst: p-benzoquinone.

发现阴离子钌配合物对生物乙醇转化为 1-丁醇和高级醇的催化活性取决于咪唑鎓反离子。在确定了涉及析氢催化剂的平行反应后，通过添加对苯醌作为助催化剂，转化率和选择性得到显着提高。该催化系统避免了副反应并导致了高达 88% 的高度竞争性转化（0.2% mol 钌催化剂负载，1.5% mol 苯醌负载）。丁醇和高级醇的产率高达 85%（总选择性 97%），作为高级生物燃料和润滑剂应用的有价值醇的混合物。催化系统可以循环使用，即使在大量水存在的情况下，反应在实际基质（来自葡萄酒生产链废物的酒精）上也表现出相当的效率，从而关闭了一个假设的经济循环。提出了最有前途的钌配合物与最有效的助催化剂对苯醌合作的反应机制。