Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Castellón, Spain.
Chemistry. 2011 Mar 28;17(14):3963-7. doi: 10.1002/chem.201002907. Epub 2011 Mar 1.
Two new water-soluble [IrI(2)(AcO)(bis-NHC)] complexes (NHC=N-heterocyclic carbene) incorporating a sulfonate functionality have been synthesized. The two complexes have been tested in the reduction of CO(2) with H(2) and iPrOH, and their activity has been compared with similar species without the sulfonate moiety. In both reactions, the complex with the two abnormally bound NHCs shows the best catalytic efficiencies, due to the higher σ-electron-donor character of the ligand. Remarkably, the activities obtained for the reduction of CO(2) under the transfer hydrogenation conditions are the best reported to date in terms of TON value (max. TON=2700). The two new complexes have also shown very good activity in the selective deuteration of arylamines, a process that is known to proceed through a chelate assisted N-directed process.
两种新的水溶性[IrI(2)(AcO)(双-NHC)]配合物(NHC=N-杂环卡宾)已被合成,其中包含磺酸官能团。这两种配合物已被用于 CO(2)与 H(2)和 iPrOH 的还原反应,并将其活性与没有磺酸基的类似物进行了比较。在这两种反应中,具有两个异常配位的 NHC 的配合物表现出最好的催化效率,这归因于配体的更高 σ-电子给体特性。值得注意的是,在转移加氢条件下还原 CO(2)所获得的活性是迄今为止报道的 TON 值(最高 TON=2700)最高的。这两种新的配合物在芳胺的选择性氘代反应中也表现出非常好的活性,已知该过程通过螯合辅助的 N 导向过程进行。