A Xanthene‐Based Mono‐Anionic PON Ligand: Exploiting a Bulky, Electronically Unsymmetrical Donor in Main Group Chemistry

The synthesis of a novel mono‐anionic phosphino‐amide ligand based on a xanthene backbone is reported, togetherr with the corresponding Ga(I) complex, (PON)Ga (PON = 4‐(di(2,4,6‐trimethylphenyl)phosphino)‐5‐(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene). The solid‐state structure of (PON)Ga (obtained from X‐ray crystallography) reveals very weak O⋅⋅⋅Ga and P⋅⋅⋅Ga interactions, consistent with a R(2)NGa fragment which closely resembles those found in one‐coordinate amidogallium systems. Strong N‐to‐Ga π donation from the amido substituent is reflected in a very short N−Ga distance (1.961(2) Å), while the P⋅⋅⋅Ga contact (3.076(1) Å) is well outside the sum of the respective covalent radii. While the donor properties of the PON ligand towards Ga(I) are highly unsymmetrical, oxidation to Ga(III) leads to much stronger coordination of the pendant phosphine as shown by P−Ga distances which are up to 20 % shorter. From a steric perspective, the PON ligand is shown to be significantly bulkier than related β‐diketiminate systems, a finding consistent with reactions of (PON)Ga towards O‐atom sources that proceed without oligomerization. Despite this, the enhanced P‐donor properties brought about by oxidation at gallium are not sufficient to quench the reactivity of the highly polar Ga−O unit. Instead, intramolecular benzylic C−H activation is observed across the Ga−O bond of a transient gallanone intermediate.