Abstract
Simple Ti amide complexes are shown to act as sources for masked Ti(II) intermediates via several pathways, as demonstrated through the investigation of a unique Ti-catalyzed nitrene-coupled transfer hydrogenation of 3-hexyne. This reaction proceeds through reduction of azobenzene by a masked Ti(II) catalyst, wherein both amines and 3-hexyne can serve as the hydrogen source/reductant for Ti by forming putative titanaziridines via β-H abstraction or putative titanacyclopentynes via protonolysis, respectively.