The structures and charge distributions of Lewis and complexes of butane-2,3-dione, 1, cyclohexane-1,2-dione, 2, and 2-methoxycyclohex-2-en-1-one, 5, have been investigated by 1H nmr spectroscopy. A 1:1 complex was formed between 1 and SnCl4 which appeared to have a bridged structure. In the case of 2 and 5 both oxygens were again involved in complex formation with TiCl4 or SnCl4. In each case the large downfield shift of the vinyl proton resonance, H3, indicated extensive charge delocalization within the complexes and that these systems can be regarded as complexed α,β-unsaturated enones. The reactions of Lewis acid complexes of 2, 5, and the silyl ethers 2-(trimethylsiloxy)cyclohex-2-en-1-one, and 3-(trimethylsiloxy)-but-3-en-2-one, 11, with butadiene have been investigated. The acyclic enol ether 11 reacted with butadiene in the presence of either TiCl4 or SnCl4 to give products corresponding to both 4C + 3C and 4C + 2C cycloaddition reactions; in all other cases 4C + 2C products only could be isolated.