Synthesis and characterization of isostructural annulated actinocenes†
ab
Jacob A.
Branson,
ab
Sheridon N.
Kelly,
ab
Asmita
Sen,
c
S. Olivia
Gunther,
a
Appie
Peterson,
a
Patrick W.
Smith,
a
Erik T.
Ouellette,
ab
John
Arnold,
ab
Jochen
Autschbach
*c
and
Stefan G.
Minasian
*a
Abstract
An isostructural series of four annulated actinocene complexes, M(hdcCOT)2 (M = Th, U, Np, Pu), is reported. The syntheses proceed through a trivalent starting material when M = U, Np, Pu with subsequent oxidation or, in the case of M = Th, directly from ThCl4(DME)2. X-ray crystallography shows that each actinocene has C2h molecular point symmetry in the solid state, with the metal atoms symmetrically bonded to two 10π-aromatic [8]annulene dianion rings. UV-Vis spectroscopy shows bands that were assigned as ligand-to-metal charge transfer (LMCT) transitions with the aid of time-dependent density functional theory (TDDFT) calculations. Compared to the M(COT)2 analogs, the LMCT transitions for M(hdcCOT)2 are red-shifted by ∼0.1 eV for all four metals. These actinocenes may be readily synthesized and crystallized even on the milligram scale (≤1 mg of metal ion content), which will enable future studies of the organometallic chemistry of transplutonium elements.
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