Abstract
Highly specific reactions of a catechol phosphane (2, H2L) with suitable ruthenium precursors afforded complexes [Ru(LH2)2Cl2], [Ru(LH)2(L′)x] (L′ = NO, PPh3, Cl, py, CNtBu) or [Ru(LH)3]Y (Y = H, K), in which 2 acts as P,O‐bound chelating ligand. The formation of bis‐ or tris‐chelate structures depends on the metal‐to‐ligand ratio employed. All products were characterized by analytical and spectroscopic data and single‐crystal XRD studies. The orientation of the neutral and mono‐deprotonated catechol groups is strongly influenced by hydrogen bonding, and the free hydroxyl groups in some complexes are pre‐organized for coordination of a second metal centre, and this suggests that these species can be used as metalloligands. This hypothesis was verified by the synthesis of heterobimetallic Ru,Ti complexes through reactions of selected metalloligands with suitable TiIV precursors. Characterization of the products by single‐crystal XRD studies revealed that the bimetallic complexes contain cores of two face‐sharing metal‐centred octahedra, which are linked by two and three ditopic ligands, respectively.
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