The synthesis, characterization, and reactivity of group 4 organometallics supported by听尾听鈥恉iketonates is reported. Sterically hindered听尾听鈥恉iketonates, such as 2,6鈥恉imesitylbenzoyl pinacolone (L1听) and 2,6鈥恉imesitylbenzoyl acetylmesitylene (L2听), preclude the formation of tetrakis鈥� and tris鈥恈helates, halting at听cis听鈥恛ctahedrally coordinated M(Ln听)2Cl2听(M = Ti, Zr, Hf;听Ln听=听L1听,听L2听). Metathesis with benzylmagnesium chloride affords M(Ln听)2Bn2听(M = Zr, Hf) and the reduced Ti(L1听)2Bn(THF) species. These are the first structurally鈥恈haracterized metal alkyl complexes exclusively supported by听尾听鈥恉iketonates among the group 4 metals. Thermolysis of Zr(Ln听)2Bn2听complexes results in unimolecular migratory insertion reaction, forming an enone by鈥恜roduct and ZrO2. Combined Eyring analyses and computational investigations suggest the bond rearrangements are initiated by an initial benzyl migration reaction to the less hindered carbonyl group on the ligand. Activation of M(Ln听)2Bn2听(M = Zr, Hf) in the presence of olefins resulted in similar oxygen abstraction. Implications and prospects for听尾听鈥恉iketonate鈥恠upported catalysis are discussed.