The synthesis, characterization, and reactivity of group 4 organometallics supported by β ‐diketonates is reported. Sterically hindered β ‐diketonates, such as 2,6‐dimesitylbenzoyl pinacolone ( L 1 ) and 2,6‐dimesitylbenzoyl acetylmesitylene ( L 2 ), preclude the formation of tetrakis‐ and tris‐chelates, halting at cis ‐octahedrally coordinated M( L n )...