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 R₂NGa 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.