Our second research direction targets activation and functionalization of small molecules using middle and late first-row transition metal (Cr-Ni) complexes in sterically encumbered bis(alkoxide) ligand environments (see structures below). We have shown that the combination of high electronegativity and strong pi-donor capability of the alkoxides makes multiply-bonded imido ligands M(OR)2= NR' platforms (M = Cr, Fe) highly reactive. Specifically, our Fe bis(alkoxide) complex can catalytically couple nitrenes from aryl azides to give azoarenes. Additionally, our Cr bis(alkoxide) dimer can catalytically form carbodiimides via reaction with azides and isocyanides. Both catalytic processes proceed through reactive metal-imido intermediates. Finally, we have also explored the synthesis of metal carbene complexes with our system, These endeavors have led to the isolation of a stable high-valent Co carbene complex, the first of its kind. Currently we are further exploring the chemistry of metal-ligand multiple bonds in our bis(alkoxide) system, toward the discovery of new types of catalysis. We are also investigating the synthesis of even bulkier alkoxide ligands and testing the reactivity of their respective bis(alkoxide) complexes. For highlights of the alkoxide project, see below.