Methanol Dehydrogenation by Iridium N-Heterocyclic Carbene Complexes
Methanol Dehydrogenation by Iridium N-Heterocyclic Carbene Complexes
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DOI：
10.1021/ic502521c
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发表时间：
2015-06-01
影响因子：
4.6
通讯作者：
Crabtree, Robert H.
中科院分区：
文献类型：
--
作者：
Campos, Jesus;Sharninghausen, Liam S.;Crabtree, Robert H.
一系列均相铱双（N-杂环卡宾）催化剂对涉及甲醇活化的三种转化具有活性：无受体脱氢、转移氢化和胺单烷基化。无受体脱氢反应需要碱，产生甲酸盐和碳酸盐，以及2-3当量的H-2。在已知用于该反应的少数均相体系中，我们的催化剂耐受空气并采用简单的配体。酮和亚胺从甲醇的转移氢化也是可能的。最后，苯胺的N-单甲基化通过“借氢”反应发生。值得注意的是，该反应对单甲基化产物具有高度选择性。
A series of homogeneous iridium bis(N-heterocyclic carbene) catalysts are active for three transformations involving dehydrogenative methanol activation: acceptorless dehydrogenation, transfer hydrogenation, and amine monoalkylation. The acceptorless dehydrogenation reaction requires base, yielding formate and carbonate, as well as 2-3 equivalents of H-2. Of the few homogeneous systems known for this reaction, our catalysts tolerate air and employ simple ligands. Transfer hydrogenation of ketones and imines from methanol is also possible. Finally, N-monomethylation of anilines occurs through a "borrowing hydrogen" reaction. Notably, this reaction is highly selective for the monomethylated product.