Reaction between a neutral beta-enamineimine ligand (nacnacH) and Me4Pt2(mu-SMe2)(2) in diethyl ether results in dehydrogenation of the solvent to form the Pt(II) olefin hydride complex (nacnac)Pt(ethyl vinyl ether)(H). Activation of ethers is kinetically favored over activation of alkanes. The KIE for ether activation (2.2) is significantly lower than that for pentane activation (3.8), indicating that initial coordination through oxygen is the likely pathway for ether activation. Marginal catalytic transfer dehydrogenation of diethyl ether and THF was achieved by heating (nacnac)Pt(neohexene)(H) at 50 degrees C for several days with excess neohexene acting as a hydrogen acceptor.