Diverging Reactivity in Anilidophosphine Supported Group III Complexes

We report the synthesis of scandium and yttrium halide complexes with bidentate, monoanionic anilidophosphine (PN) ligands and the general formula (PN)₂MX (M = Sc (1-X), Y (2-X); X = Cl (1-Cl/2-Cl), X = I (1-I/2-I). Attempts to functionalize these complexes by salt metathesis reaction revealed that the chlorido complexes are quite unreactive precursors, whereas the iodo complexes readily engage in a broad variety of reactions. We report the azide complexes (1-N₃ and 2-N₃) as well as the heavy cyanate complexes with the general formula (PN)₂M(OCPn) (M = Sc; Pn = P (1-OCP), Pn = As (1-OCAs) and M = Y; Pn = P (2-OCP), Pn = As (2-OCAs)). Furthermore, the amido and phosphanido complexes of the general formula (PN)₂M(PnHMesityl) with Pn = N (1-NHMes, 2-NHMes) and Pn = P (1-PHMes, 2-PHMes) are reported. Attempts to synthesize benzyl complexes of the general type (PN)₂M(Benzyl) with M = Sc, Y, La revealed drastic differences in the reactivity of the group III metal ions. While the scandium and yttrium complexes displayed elimination of KPN without the formation of defined metal complexes, for lanthanum, defined C-H activation chemistry has been observed, yielding -ate complex 3-CH.