When electron-deficient alkynes reacted with η 4 -(vinylketenimine)iron complexes, pyrroles were produced. Pyrrole formation involved the [2 + 3] cycloaddition of alkyne to the ketenimine moiety, migration of the vinyl group, and decomplexation. Either alkynes bearing two electron-withdrawing groups, or terminal alkynes with an electron-withdrawing group reacted to generate pyrroles. * sı Supporting InformationThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.organomet.1c00321.Experimental details; 1 H NMR and 13 C NMR spectra; X-ray crystallographic data for 4a and 2l (PDF)Accession CodesCCDC 2074661 and 2074664 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk