Gauging electronic dissymmetry in bis-chelates of titanium(<scp>iv</scp>) using sterically and electronically variable 2,2′-biphenoxides

3,3′,5,5′-Tetrasubstituted-2,2′-biphenolate complexes of titanium(IV) with bis(diketonate) (Bob), bis(hydroxamate) (Hox) and mixed diketonate–hydroxamate (Hob) ligands have been prepared from the corresponding diisopropoxide complexes. Four of the twelve compounds have been characterized crystallographically, and in the solid state all show the (Δ,R)/(Λ,S) relative stereochemistry at titanium and the biaryloxide, respectively, as previously observed in (acac)2Ti(1,1′-bi-2-naphtholate) complexes. In solution the compounds epimerize by atropisomerization of the biphenolate moiety with ΔG‡ ≈ 14 kcal mol−1. The bis(diketonate) complexes show high diastereoselectivity except for the most electron-poor tetranitrobiphenolate. In contrast, the bis(hydroxamate) shows low to moderate selectivity which correlates with the steric but not electronic properties of the biphenolates (Br < CH3 < NO2 < tBu). The mixed diketonate–hydroxamate complexes show intermediate behaviour. These observations are rationalized on the basis of MO arguments regarding ligand-metal π bonding. Symmetrical chelates such as diketonates foster mixing of two dπ orbitals and create a dissymmetric electronic environment. This mixing does not take place with unsymmetrical ligands such as hydroxamates, which therefore do not create an environment where electronic effects contribute significantly to binding stereoselectivity.