Insertion Reactions and Catalytic Hydrophosphination of Heterocumulenes using α‑Metalated N,N‑Dimethylbenzylamine Rare-Earth-Metal Complexes
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The reactivity of homoleptic α-metalated dimethylbenzylamine lanthanide complexes (α-Ln(DMBA)3; Ln = La, Y; DMBA = α-deprotonated dimethylbenzylamine) was probed through a series of stoichiometric insertion and catalytic hydrophosphination reactions. Both rare-earth-metal species inserted 3 equiv of various carbodiimides to form the corresponding homoleptic amidinates. α-La(DMBA)3 was also found to be a useful precatalyst for the room-temperature hydrophosphination of heterocumulenes to form phosphaguanidines, phosphaureas, and phosphathioureas in moderate to excellent isolated yields. Furthermore, through a series of stepwise stoichiometric protonation and insertion reactions, a plausible mechanism for the hydrophosphination catalysis was investigated.
