University of Wisconsin-La Crosse, 1725 State Street, La Crosse, WI 54601, USA.
Dalton Trans. 2011 Jun 14;40(22):5921-5. doi: 10.1039/c1dt10147a. Epub 2011 May 3.
We have examined the catalytic activity of an iron(III) complex bearing the 14,28-[1,3-diiminoisoindolinato]phthalocyaninato (diiPc) ligand in oxidation reactions with three substrates (cyclohexane, cyclooctane, and indan). This modified metallophthalocyaninato complex serves as an efficient and selective catalyst for the oxidation of cyclohexane and cyclooctane, and to a far lesser extent indan. In the oxidations of cyclohexane and cyclooctane, in which hydrogen peroxide is employed as the oxidant under inert atmosphere, we have observed turnover numbers of 100.9 and 122.2 for cyclohexanol and cyclooctanol, respectively. The catalyst shows strong selectivity for alcohol (vs. ketone) formation, with alcohol to ketone (A/K) ratios of 6.7 and 21.0 for the cyclohexane and cyclooctane oxidations, respectively. Overall yields (alcohol + ketone) were 73% for cyclohexane and 92% for cyclooctane, based upon the total hydrogen peroxide added. In the catalytic oxidation of indan under similar conditions, the TON for 1-indanol was 10.1, with a yield of 12% based upon hydrogen peroxide. No 1-indanone was observed in the product mixture.
我们研究了一种铁（III）配合物的催化活性，该配合物带有 14,28-[1,3-二亚氨基异吲哚啉基]酞菁（diiPc）配体，用于三种底物（环己烷、环辛烷和茚满）的氧化反应。这种修饰的金属酞菁配合物是环己烷和环辛烷氧化的有效和选择性催化剂，而对茚满的催化作用则要小得多。在以过氧化氢为氧化剂、在惰性气氛下进行的环己烷和环辛烷氧化反应中，我们观察到环己醇和环辛醇的转化率分别为 100.9 和 122.2。该催化剂对醇（相对于酮）的生成具有很强的选择性，环己烷和环辛烷氧化的醇/酮（A/K）比分别为 6.7 和 21.0。基于添加的总过氧化氢，环己烷的总收率（醇+酮）为 73%，环辛烷的总收率为 92%。在类似条件下，吲哚的催化氧化中，1-吲哚醇的 TON 为 10.1，基于过氧化氢的产率为 12%。产物混合物中未观察到 1-茚酮。
