Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
J Am Chem Soc. 2022 Nov 9;144(44):20243-20248. doi: 10.1021/jacs.2c10087. Epub 2022 Oct 27.
The synthesis and reactivity of an ambiphilic iridium complex IrCl(PPh)() (; = P(N(-N(2-pyridyl)CH))) featuring a chelating nontrigonal phosphorus triamide ligand is reported. The tandem Lewis basic Ir and Lewis acidic P of achieve a two-site oxidative addition of phenol giving the iridaphenoxyphosphorane species IrHCl(PPh)() (). In contrast, reactions of with benzenethiol and benzeneselenol do not engage and instead proceed via metal-centered oxidative addition of the chalcogen-hydrogen bond. These findings establish metal-ligand cooperation involving nonspectator reactivity of tricoordinate phosphorus ligands.
本文报道了一种双亲和性铱配合物 IrCl(PPh)()(; = P(N(-N(2-吡啶基)CH))) 的合成与反应活性,该配合物具有螯合非三角磷三酰胺配体。通过实现酚的两部位路易斯碱 Ir 和路易斯酸 P 的协同氧化加成,生成了 IrHCl(PPh)() () 型的铱苯氧膦络合物。相比之下,与苯硫酚和苯硒酚的反应并不涉及,而是通过硫/硒-氢键的金属中心氧化加成进行。这些发现确立了涉及三配位磷配体非 spectator 反应性的金属-配体协同作用。