TY - JOUR
T1 - A Terminal Neptunium(V)-Mono(Oxo) Complex
AU - Dutkiewicz, Michal S.
AU - Goodwin, Conrad
AU - Perfetti, Mauro
AU - Gaunt, Andrew J.
AU - Griveau, Jean-Christophe
AU - Colineau, Eric
AU - Kovács, Attila
AU - Wooles, Ashley J.
AU - Caciuffo, Roberto
AU - Walter, Olaf
AU - Liddle, Stephen T.
PY - 2022/3/1
Y1 - 2022/3/1
N2 - Neptunium was the first actinide element to be artificially synthesized, yet, compared with its more famous neighbours uranium and plutonium, is less conspicuously studied. Most neptunium chemistry involves the neptunyl di(oxo)-motif, and transuranic compounds with one metal–ligand multiple bond are rare, being found only in extended-structure oxide, fluoride or oxyhalide materials. These combinations stabilize the required high oxidation states, which are otherwise challenging to realize for transuranic ions. Here we report the synthesis, isolation and characterization of a stable molecular neptunium(V)–mono(oxo) triamidoamine complex. We describe a strong Np≡O triple bond with dominant 5f-orbital contributions and σ
u > π
u energy ordering, akin to terminal uranium-nitrides and di(oxo)-actinyls, but not the uranium–mono(oxo) triple bonds or other actinide multiple bonds reported so far. This work demonstrates that molecular high-oxidation-state transuranic complexes with a single metal–ligand bond can be stabilized and studied in isolation. [Figure not available: see fulltext.]
AB - Neptunium was the first actinide element to be artificially synthesized, yet, compared with its more famous neighbours uranium and plutonium, is less conspicuously studied. Most neptunium chemistry involves the neptunyl di(oxo)-motif, and transuranic compounds with one metal–ligand multiple bond are rare, being found only in extended-structure oxide, fluoride or oxyhalide materials. These combinations stabilize the required high oxidation states, which are otherwise challenging to realize for transuranic ions. Here we report the synthesis, isolation and characterization of a stable molecular neptunium(V)–mono(oxo) triamidoamine complex. We describe a strong Np≡O triple bond with dominant 5f-orbital contributions and σ
u > π
u energy ordering, akin to terminal uranium-nitrides and di(oxo)-actinyls, but not the uranium–mono(oxo) triple bonds or other actinide multiple bonds reported so far. This work demonstrates that molecular high-oxidation-state transuranic complexes with a single metal–ligand bond can be stabilized and studied in isolation. [Figure not available: see fulltext.]
U2 - 10.1038/s41557-021-00858-0
DO - 10.1038/s41557-021-00858-0
M3 - Article
VL - 14
SP - 342
EP - 349
JO - Nature Chemistry
JF - Nature Chemistry
SN - 1755-4330
IS - 3
ER -