Facile oxidative addition of water at iridium: reactivity of trans-[Ir(4-C5NF4)(H)(OH)(PiPr3)2] towards CO2 and NH3

Abstract

A reaction of trans-[Ir(4-C₅NF₄)(η²-C₂H₄)(PiPr₃)₂] (1) with an excess of water in THF at room temperature affords the hydrido hydroxo complex trans-[Ir(4-C₅NF₄)(H)(OH)(PiPr₃)₂] (2). Treatment of 2 with CO furnishes trans-[Ir(4-C₅NF₄)(H)(OH)(CO)(PiPr₃)₂] (3). Reductive elimination of water from 3 leads to the formation of the iridium(I) carbonyl complex trans-[Ir(4-C₅NF₄)(CO)(PiPr₃)₂] (4). The insertion of CO₂ into the Ir–O bond of 2 forms the hydrido hydrogencarbonato complex trans-[Ir(4-C₅NF₄)(H)(κ²-(O,O)-O₂COH)(PiPr₃)₂] (5). Treatment of 2 with NH₃ in C₆D₆ yields trans-[Ir(4-C₅NF₄)(H)(OH)(NH₃)(PiPr₃)₂] (6). Storage of the reaction mixture at room temperature reveals the formation of the N–H activation product [Ir(4-C₅NF₄)(H)(μ-NH₂)(NH₃)(PiPr₃)]₂ (7).