From π Bonds without σ Bonds to the Longest Metal–Metal Bond Ever: A Survey on Actinide–Actinide Bonding in Fullerenes
Result description
Actinide-actinide bonds are rare. Only a few experimental systems with An-An bonds have been described so far. Recent experimental characterization of the U2@Ih(7)-C80 (J. Am. Chem. Soc. 2018, 140, 3907) system with one-electron two-center (OETC) U-U bonds as was predicted by some of us (Phys. Chem. Chem. Phys. 2015, 17, 24182) encourages the search for more examples of actinide-actinide bonding in fullerene cages. Here, we investigate actinide-actinide bonding in An2@D5h(1)-C70, An2@Ih(7)-C80, and An2@D5h(1)-C90 (An = Ac-Cm) endohedral metallofullerenes (EMFs). Using different methods of the chemical bonding analysis, we show that most of the studied An2@C70 and An2@C80 systems feature one or more one-electron two-center actinide-actinide bonds. Unique bonding patterns are revealed in plutonium EMFs. The Pu2@Ih(7)-C80 features two OETC Pu-Pu π bonds without any evidence of a corresponding σ bond. In the Pu2@D5h(1)-C90 with rPu-Pu = 5.9 Å, theory predicts the longest metal-metal bond ever described. Predicted systems are thermodynamically stable and should be, in principle, experimentally accessible, though radioactivity of studied metals may be a serious obstacle.
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The result's identifiers
Result code in IS VaVaI
Result on the web
DOI - Digital Object Identifier
Alternative languages
Result language
angličtina
Original language name
From π Bonds without σ Bonds to the Longest Metal–Metal Bond Ever: A Survey on Actinide–Actinide Bonding in Fullerenes
Original language description
Actinide-actinide bonds are rare. Only a few experimental systems with An-An bonds have been described so far. Recent experimental characterization of the U2@Ih(7)-C80 (J. Am. Chem. Soc. 2018, 140, 3907) system with one-electron two-center (OETC) U-U bonds as was predicted by some of us (Phys. Chem. Chem. Phys. 2015, 17, 24182) encourages the search for more examples of actinide-actinide bonding in fullerene cages. Here, we investigate actinide-actinide bonding in An2@D5h(1)-C70, An2@Ih(7)-C80, and An2@D5h(1)-C90 (An = Ac-Cm) endohedral metallofullerenes (EMFs). Using different methods of the chemical bonding analysis, we show that most of the studied An2@C70 and An2@C80 systems feature one or more one-electron two-center actinide-actinide bonds. Unique bonding patterns are revealed in plutonium EMFs. The Pu2@Ih(7)-C80 features two OETC Pu-Pu π bonds without any evidence of a corresponding σ bond. In the Pu2@D5h(1)-C90 with rPu-Pu = 5.9 Å, theory predicts the longest metal-metal bond ever described. Predicted systems are thermodynamically stable and should be, in principle, experimentally accessible, though radioactivity of studied metals may be a serious obstacle.
Czech name
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Czech description
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Classification
Type
Jimp - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
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Volume of the periodical
59
Issue of the periodical within the volume
17
Country of publishing house
US - UNITED STATES
Number of pages
8
Pages from-to
12608-12615
UT code for WoS article
000570979900079
EID of the result in the Scopus database
2-s2.0-85090488139
Result type
Jimp - Article in a specialist periodical, which is included in the Web of Science database
OECD FORD
Inorganic and nuclear chemistry
Year of implementation
2020