2023
DOI: 10.1002/anie.202215846
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Bonding and Reactivity in Terminal versus Bridging Arenide Complexes of Thorium Acting as ThII Synthons

Abstract: Thorium redox chemistry is extremely scarce due to the high stability of ThIV. Here we report two unique examples of thorium arenide complexes prepared by reduction of a ThIV‐siloxide complex in presence of naphthalene, the mononuclear arenide complex [K(OSi(OtBu)3)3Th(η6‐C10H8)] (1) and the inverse‐sandwich complex [K(OSi(OtBu)3)3Th]2(μ‐η6,η6‐C10H8)] (2). The electrons stored in these complexes allow the reduction of a broad range of substrates (N2O, AdN3, CO2, HBBN). Higher reactivity was found for the compl… Show more

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Cited by 17 publications
(26 citation statements)
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“…Upon reaction of diazoalkene 44 A with the thorium arene precursor 91 the Th IV amido acetylido complex 92 could be isolated (Scheme 24). [76] …”
Section: Room‐temperature‐stable Diazoalkenesmentioning
confidence: 99%
See 1 more Smart Citation
“…Upon reaction of diazoalkene 44 A with the thorium arene precursor 91 the Th IV amido acetylido complex 92 could be isolated (Scheme 24). [76] …”
Section: Room‐temperature‐stable Diazoalkenesmentioning
confidence: 99%
“…Upon reaction of diazoalkene 44 A with the thorium arene precursor 91 the Th IV amido acetylido complex 92 could be isolated (Scheme 24). [76] The unusual cleavage of the imidazole heterocyclic backbone was computationally investigated and is likely to be a result of the reduction of the diazoalkene by the Thprecursor. A Th-vinylidene intermediate is computationally proposed as transient intermediate, but could not be spectroscopically identified.…”
Section: Metal Vinylidene Precursorsmentioning
confidence: 99%
“…Bei der Reaktion von Diazoalken 44 A mit dem Thoriumaren‐Vorläufer 91 konnte der Th IV ‐Amido‐Acetylido‐Komplex 92 isoliert werden (Schema 24). [76] …”
Section: Raumtemperaturstabile Diazoalkeneunclassified
“…Bei der Reaktion von Diazoalken 44 A mit dem Thoriumaren-Vorläufer 91 konnte der Th IV -Amido-Acetylido-Komplex 92 isoliert werden (Schema 24). [76] Die ungewöhnliche Spaltung des heterocyclischen Imidazol-Rückgrats wurde rechnerisch untersucht und ist wahrscheinlich auf die Reduktion des Diazoalkens durch den Th-Vorläufer zurückzuführen. Ein Th-Vinylidenzwischenprodukt wird rechnerisch als reaktives Intermediat vorgeschlagen, konnte aber spektroskopisch nicht identifiziert werden.…”
Section: Metal-vinyliden Vorläuferverbindungenunclassified
“…Main group and transition metal polyarene complexes have been studied for a variety of polyarenes with different degrees of reduction and coordination modes (Figure b), ,, together with reactivity , and electronic properties . Albeit rarer, rare-earth metal complexes of reduced anthracene, pyrene, and tetracene anions have been reported. In contrast, while uranium is prone to form inverse-sandwich structures with benzene and substituted benzenes, featuring δ bonding interactions, actinide polyarene complexes are scarce and mostly limited to naphthalene. , Only recently, Fortier and co-workers reported the synthesis of π-bound uranium anthracene complexes (Figure c). , The lack of uranium polyarene complexes and their potential applications in synthesis and material sciences prompted us to explore the possible formation of uranium polyarene complexes with a variety of polyarenes. Herein, we report the synthesis and characterization of a series of uranium polyarene complexes, with the number of fused rings ranging from three to five.…”
Section: Introductionmentioning
confidence: 99%