Rare‐Earth Metal Complexes with Terminal Imido Ligands

Abstract

Imide complexes [(TptBu,Me)Y(=NC6H3Me2‐2,6)(DMAP)] and [(TptBu,Me)Lu{=NC6H3(CF3)2‐3,5}(DMAP)] were obtained by Lewis base induced methane elimination of the corresponding methyl/anilide complexes, which were synthesized from [(TptBu,Me)LuMe2] and [(TptBu,Me)YMe(GaMe4)], respectively. Terminal Ln=N bonding is evidenced by very short Ln–N distances [min. 1.993(5) Å] and almost linear Ln–N–C(aryl) bond angles.

Formation of a Ce(IV) Oxo Complex via Inner Sphere Nitrate Reduction

“…15 More recently, Anwander and co-workers reported the preparation of the first terminal lanthanide imido complexes, [Tp tBu,Me )Ln(=NAr)(dmap)] (Ln = Y, Ar = 2,6-Me 2 C 6 H 3 ; Ln = Lu, Ar = 3,5-(CF 3 ) 2 C 6 H 3 ). 16 This was followed by the synthesis of a cerium(IV) terminal imido, [K(DME) 2 ][Ce=N(3,5-(CF 3 ) 2 C 6 H 3 )(TriNOx)], by Schelter and co-workers. 17 Also of note is the Ce(IV) methanediide complex, [Ce(BIPM TMS )(ODipp) 2 ] (BIPM TMS = C(PPh 2 NSiMe 3 ) 2 ; Dipp = C 6 H 3 -2,6-i Pr 2 ), reported by Liddle and co-workers.…”

Molecular Pnictogen Activation by Rare Earth and Actinide Complexes

“…Related to this, the understanding of the nature of bonding of Ln-N multiple bonds is of fundamental interest and the isolation of terminal imido (Ln=NR) complexes has only recently been reported [162][163][164]. It is also significant to consider the reactivity of Ln-N2 complexes in the context of other low electron count early transition metal complexes; here, N2 cleavage or functionalisation can be achieved through ligand induced reductive cleavage [165][166][167][168][169][170][171][172][173], and more generally, N-N bond scission of reduced N2 derivatives can be attained through metal-ligand cooperativity [174,175].…”

Piano-Stool Lutetium Amido and Imido Compounds Supported by a Constrained Bis(oxazoline)cyclopentadienyl Ligand

“…10 This strategy provides isolable or reactive imido complexes of scandium, the smallest of the rare earth elements, and it was also recently extended to lutetium in an isolated imido complex supported by the bulky tert-butyl-substituted tris(pyrazolyl)-borate ligand. 11 Instead, the "NR" moieties typically bridge between multiple metal centers in lanthanoid chemistry. For example, the polymetallic benzylimido complexes [(C 5 Me 4 SiMe 3 )Ln(μ 3 -NCH 2 Ph)] 4 (Ln = Lu, Y) form from the reaction of tetranuclear polyhydrido complexes and benzonitrile.…”