Abstract and subjects
Reaction of the terphenyl bis(anilide) ligand [{K(DME)
}
L
] (L
= {C
H
[(2,6-
Pr
C
H
)NC
H
]
}
) with trivalent chloride "MCl
" salts (M = Ce, U, Np) yields two distinct products; neutral L
M(Cl)(THF) (1
) (M = Np, Ce), and the "-ate" complexes [K(DME)
][(L
)Np(Cl)
] (2
) or ([L
M(Cl)
(μ-K(X)
)])
(2
, 2
) (M = Ce, U) (X = DME or Et
O) (2
). Alternatively, analogous reactions with the iodide [MI
(THF)
] salts provide access to the neutral compounds L
M(I)(THF) (3
) (M = Ce, U, Np, Pu). All complexes exhibit close arene contacts suggestive of
-interactions with the central arene ring of the terphenyl backbone, with 3
comprising the first structurally characterized Pu
-arene moiety. Notably, the metal-arene bond metrics diverge from the predicted trends of metal-carbon interactions based on ionic radii, with the uranium complexes exhibiting the shortest M-C
distance in all cases. Overall, the data presents a systematic study of f-element M-
-arene complexes across the early actinides U, Np, Pu, and comparison to cerium congeners.