Rare-earth metal allyl and hydrido complexes supported by an (NNNN)-type macrocyclic ligand: synthesis, structure, and reactivity toward biomass-derived furanics.

The preparation and characterization of a series of neutral rare-earth metal complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(2)] (Ln=Y, La, Ce, Pr, Nd, Sm) supported by the 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane anion (Me(3)TACD(-)) are reported. Upon treatment of the neutral allyl complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(2)] with Brønsted acids, monocationic allyl complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(thf)(2)][B(C(6)X(5))(4)] (Ln=La, Ce, Nd, X=H, F) were isolated and characterized. Hydrogenolysis gave the hydride complexes [Ln(Me(3)TACD)H(2)](n) (Ln=Y, n=3; La, n=4; Sm).

Allyl complexes of scandium: synthesis and structure of neutral, cationic and anionic derivatives.

Neutral, cationic and anionic allyl compounds of scandium contain highly fluxional allyl ligands in solution, whilst in the solid state both η(1)- and η(3)-binding modes are detected.