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 σu > πu 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.]
A terminal neptunium(V)–mono(oxo) complex / Dutkiewicz M.S.; Goodwin C.A.P.; Perfetti M.; Gaunt A.J.; Griveau J.-C.; Colineau E.; Kovacs A.; Wooles A.J.; Caciuffo R.; Walter O.; Liddle S.T.. - In: NATURE CHEMISTRY. - ISSN 1755-4330. - ELETTRONICO. - (2022), pp. 1-8. [10.1038/s41557-021-00858-0]
A terminal neptunium(V)–mono(oxo) complex
Perfetti M.;
2022
Abstract
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 σu > πu 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.]
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