Methylidene Rare-Earth-Metal Complex Mediated Transformations of CN, NN and NH Bonds: New Routes to Imido Rare-Earth-Metal Clusters

Three new patterns of reactivity of rare‐earth metal methylidene complexes have been established and thus have resulted in access to a wide variety of imido rare‐earth metal complexes [L3Ln3(μ2‐Me)3(μ3‐Me)(μ‐NR)] (L=[PhC(NC6H3iPr2‐2,6)2]−; R=Ph, Ln=Y (2 a), Lu (2 b); R=2,6‐Me2C6H3, Ln=Y (3 a), Lu (3 b); R=p‐ClC6H4, Ln=Y (4 a), Lu (4 b); R=p‐MeOC6H4, Ln=Y (5 a), Lu (5 b); R=Me2CHCH2CH2, Ln=Y (6 a), Lu (6 b)) and [{L3Lu3(μ2‐Me)3(μ3‐Me)}2(μ‐NR′N)] (R′=(CH2)6 (7 b), (C6H4)2 (8 b)). Complex 2 b was treated with an excess of CO2 to give the corresponding carboxylate complex [L3Lu3(μ‐η1:η1‐O2CCH3)3(μ‐η1:η2‐O2C‐CH3)(μ‐η1:η1:η2‐O2CNPh)] (9 b) easily. Complex 2 a could undergo the selective μ3‐Me ion reaction with phenyl acetylene to give the mixed imido/alkynide complex [L3Y3(μ2‐Me)3(μ3‐η1:η1:η3‐NPh)(μ3‐CCPh)] (10 a) in high yield. Treatment of 2 with one equivalent of thiophenol gave the selective μ3‐methyl‐ed products [L3Ln3(μ2‐Me)3(μ3‐η1:η1:η3‐NPh)(μ3‐SPh)] (Ln=Y (11 a); Lu (11 b). All new complexes have been characterized by elemental analysis, NMR spectroscopy, and most of the structures confirmed by X‐ray diffraction. New imido clusters: Three new routes for the synthesis of rare‐earth‐metal imido clusters were established based on the reactions of rare‐earth‐metal methylidene complexes with imines, azobenzenes, and amines, and resulted in access to a wide variety of imido rare‐earth‐metal complexes (an example is shown in the figure). The reaction of these imido clusters toward some small substrates gave imido derivatives.