The chemistry of metal-ligand multiple bonds is applied in catalytic transformations and bioinorganic studies. The multiply bonded terminal imido ligands are of particular interest due to their applications. While d-block metal and actinide imido reactivity is well explored, lanthanide imido reactivity is still underdeveloped, since these compounds are highly reactive and form bridging structures. Recently, our group reported a series of isolable Ce(IV) imido compounds, stabilized by a tripodal hydroxylamine ligand, TriNOx3-. These imido compounds were prepared by treating the parent anilide compound with a base. They include a series of solvent-coordinated compounds with an alkali metal capped Ce=N bond, 1-M [M(DME)2][Ce=NArF(TriNOx)] (M=K, Rb, Cs), as well as a congener with the uncapped Ce=N double bond, [Cs(2.2.2 cryptand)][Ce=NArF(TriNOx)]. The scarcity of data on the lanthanide imido performance in small molecule activation prompted us to explore the reactivity of these compounds with carbon dioxide and organic isocyanates. The insertion of carbon dioxide into the Ce=N bond of 1-Cs yielded a rare organolanthanide complex [Cs(pyr)2][Ce(OC(O)N−ArF)(TriNOx)]. No double insertion yielding a dicarbamate or decomposition into an isocyanate and a Ce(IV) oxo species was observed. The preliminary data on [Cs(2.2.2 cryptand)][Ce=NArF(TriNOx)] reactivity with carbon dioxide suggests the reactivity pattern similar to the one described above, with the single insertion of CO2 into the double bond producing an organocarbamate species. Reacting of 1-K and 1-Rb with organic isocyanates (R−NCO, R = Ad, ArF) allowed us to isolate alkali metal capped κ2-(N,O) organoureate Ce(IV) complexes. These studies demonstrate how reactivity of lanthanide imidos can be different from d-block or actinide imido chemistry.

Reactivity of Ce(IV) imido compounds with heteroallenes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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