Lithium complexes containing bidentate dianionic trityl/aryloxide ligands, Li2[ROC](Et2O)n ([ROC]2– = [κ2‐O,C‐OC6H2‐2‐C(3,5‐R2C6H3)2‐4,6‐tBu2]2–; 2a (R = H, n = 1) and 2b (R = Me, n = 0)) were synthesized through double metalation of ortho‐benzhydryl phenols with nBuLi. Similarly, sodium compound Na2[HOC](THF)2.5 (3a) was obtained when phenol H2[HOC] (1a) was treated with two equiv. of nBuLi/NaOtBu. The lithium compounds were employed for the preparation of other metal complexes supported by [ROC]2– ligands, i.e. {Zn[ROC](THF)}2 (R = H (4a) or Me (4b)), Sn[HOC]2 (5a) and Cp*Ir[MeOC] (6b, Cp* = η5‐C5Me5), by salt metathesis reactions with metal halides. The solid‐state structures of all metal complexes were established by X‐ray crystallography. The nuclearity of these metal complexes and the coordination fashion of the [ROC]2– ligands were found to be highly dependent on the identity of metal centers. Additionally, compound 2a was found to be facilely oxidized, as revealed by both electrochemical and reactivity study.

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