EaStCHEM, School of Chemistry, University of St. Andrews, Purdie Building, North Haugh, St. Andrews, Fife KY16 9ST, UK.
Chemistry. 2013 Jun 10;19(24):7904-16. doi: 10.1002/chem.201300669. Epub 2013 Apr 24.
A family of iridium(I) hydroxides of the form [Ir(cod)(NHC)(OH)] (cod = 1,5-cyclooctadiene, NHC = N-heterocyclic carbene) is reported. Single-crystal X-ray analyses and computational methods were used to explore the structural characteristics and steric properties of these new complexes. The model complex [Ir(cod)(IiPr)(OH)] (IiPr = 1,3-(diisopropyl)imidazol-2-ylidene) undergoes reaction with a wide variety of substrates including boronic acids and silicon compounds. In addition, O-H, N-H and C-H bond activation was achieved with alcohols, carboxylic acids, amines and various sp-, sp(2)- and sp(3)-hybridised carbon centres, giving access to a wide range of new Ir(I) complexes. These studies have allowed us to explore the exciting reactivity of this motif, revealing a versatile and useful synthon capable of activating important chemical bonds under mild (typically room temperature) conditions. No additives were required and, in the case of X-H bond activation, water was the only waste product, rendering this an atom efficient procedure for bond activation. This system has great potential for the construction of new catalytic cycles for organic synthesis and small-molecule activation.
报道了一种形式为[Ir(cod)(NHC)(OH)]（cod=1,5-环辛二烯，NHC=N-杂环卡宾）的铱（I）氢氧化物家族。单晶 X 射线分析和计算方法用于探索这些新配合物的结构特征和空间性质。模型配合物[Ir(cod)(IiPr)(OH)]（IiPr=1,3-（二异丙基）咪唑-2-亚基）与包括硼酸和硅化合物在内的各种底物反应。此外，通过醇、羧酸、胺和各种 sp、sp(2)-和 sp(3)-杂化碳中心实现了 O-H、N-H 和 C-H 键的活化，从而获得了广泛的新型 Ir(I)配合物。这些研究使我们能够探索这一主题激动人心的反应性，揭示了一种多功能且有用的合成子，能够在温和（通常在室温下）条件下激活重要的化学键。不需要添加剂，并且在 X-H 键活化的情况下，水是唯一的废物产物，使该方法成为一种原子经济性的键活化程序。该系统在构建有机合成和小分子活化的新催化循环方面具有巨大的潜力。
