Despite broad interest in metal carbene complexes, there remain few examples of catalytic transformations of ethers that proceed via alkoxycarbene intermediates generated by alpha,alpha-dehydrogenation. We demonstrate that both neutral and cationic alkoxycarbene derivatives are accessible via ether dehydrogenation at a PNP(iPr)(4) pincer-supported iridium complex (PNP(iPr)(4) = 2,6-bis((diisopropylphosphino)methyl)pyridine). Both cationic and neutral alkoxycarbene complexes undergo group transfer imination with azides, with the cationic derivative serving as a more efficient catalyst for cyclopentyl ether imination. Mechanistic studies support an iridium(I)dinitrogen complex as the resting state in the dark and a role for light-promoted N-2 dissociation. Isoamyl nitrite and phenyl ethyl ketene are also found to engage with the cationic alkoxycarbene complex in formal alkoxide and O atom transfer reactions, respectively. In the former case an isolable dialkoxyalkyliridium complex is obtained, representing only the second example of a structurally characterized dialkoxyalkyl complex of a transition metal.