Recent advances in heterometallic clusters with f-block metal–metal bonds: synthesis, reactivity and applications

Fang, Wei; Zhu, Qin; Zhu, Congqing

doi:10.1039/d2cs00424k

Cited by 26 publications

(23 citation statements)

References 76 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The nature of the interaction is not very different from that observed in classical organometallic ligands. 31,32,[49][50][51] Finally, we have analysed the hypothetical system Pa@C 27 B, isoelectronic to U@C 27 B + with a closed-shell structure. Protactinium, with a very similar size as U, has the same spatial constraints and it is placed at the centre of the cage interacting with boron and all the carbon atoms in a quite similar way.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Highly oxidized U(vi) within the smallest fullerene: gas-phase synthesis and computational study of boron-doped U@C₂₇B

Vicente

Alias

Dunk

et al. 2023

Inorg. Chem. Front.

View full text Add to dashboard Cite

show abstract

Section: Resultsmentioning

confidence: 99%

“…The nature of the interaction is not very different from that observed in classical organometallic ligands. 31,32,49–51…”

Section: Resultsmentioning

confidence: 99%

Highly oxidized U(vi) within the smallest fullerene: gas-phase synthesis and computational study of boron-doped U@C₂₇B

Vicente

Alias

Dunk

et al. 2023

Inorg. Chem. Front.

View full text Add to dashboard Cite

show abstract

“…We envisioned that the rare-earth metal ions are suitable for metalloligands due to their adjustable Lewis acidity according to the variation of ionic radii from Sc(III) (0.745 Å) to La(III) (1.032 Å), which would provide an interesting electronic perturbation via a flexible M → Ln bonding interaction . Although success was achieved recently with the assembly of Ln(III/II)–M(0) (M = Ni, Pd, Pt) complexes that exhibited M → Ln dative interactions and heterobimetallic reactivities, , profound challenges exist with Ln–Co complexes, probably due to the highly oxo-, halophilic property of the hard Ln(III) ions, and the shortage of suitable low-valent cobalt precursors in contrast to those commercially available for Ni(0) and Pd(0). To the best of our knowledge, the closest system achieved so far is a Zr(IV)–Co(−I) complex (Figure C) and its Ti analogue, and the complex featuring a Ln–Co bond has not been reported.…”

Section: Introductionmentioning

confidence: 99%

Dinitrogen Complexes of Cobalt(−I) Supported by Rare-Earth Metal-Based Metalloligands

Zhang

Pan

et al. 2023

Inorg. Chem.

View full text Add to dashboard Cite

Sequential reactions of heptadentate phosphinoamine LH 3 with rare-earth metal tris-alkyl precursor (Me 3 SiCH 2 ) 3 Ln-(THF) 2 (Ln = Sc, Lu, Yb, Y, Gd) and a low-valent cobalt complex (Ph 3 P) 3 CoI afforded rare-earth metal-supported cobalt iodide complexes. Reduction of these iodide complexes under N 2 allowed the isolation of the first series of dinitrogen complexes of Co(−I) featuring dative Co(−I) → Ln (Ln = Sc, Lu, Yb, Y, Gd) bonding interactions. These compounds were characterized by multinuclear NMR spectroscopy, X-ray diffraction analysis, electrochemistry, and computational studies. The correlation of N−N vibrational frequencies with the pK a of [Ln(H 2 O) 6 ] 3+ showed that strongest activation of N 2 was achieved with the least Lewis acidic Gd(III) ion. Interestingly, these Ln−Co−N 2 complexes catalyzed silylation of N 2 in the presence of KC 8 and Me 3 SiCl with turnover numbers (TONs) up to 16, where the lutetium-supported Co(−I) complex showed the highest activity within the series. The role of the Lewis acidic Ln(III) was crucial to achieve catalytic turnovers and tunable reactivity toward N 2 functionalization.

show abstract

“…In organometallic chemistry, the metal−metal interactions with participation of f-block elements have attracted the interest of experimentalists and theoreticians. 35 Numerous compounds have been reported containing metal−metal bonds between a Ln (or An) and a TM, and also between two Ln ions. In some bimetallic clusters with An−TM bonds, the presence of a weak direct U−U interaction has been proposed, as occurs in recently reported systems with four (or six) U−Ni bonds.…”

Section: ■ Introductionmentioning

confidence: 99%

Are U–U Bonds Inside Fullerenes Really Unwilling Bonds?

et al. 2023

View full text Add to dashboard Cite

Previous characterizations of diactinide endohedral metallofullerenes (EMFs) Th 2 @C 80 and U 2 @C 80 have shown that although the two Th 3+ ions form a strong covalent bond within the carbon cage, the interaction between the U 3+ ions is weaker and described as an "unwilling" bond. To evaluate the feasibility of covalent U−U bonds, which are neglected in classical actinide chemistry, we have first investigated the formation of smaller diuranium EMFs by laser ablation using mass spectrometric detection of dimetallic U 2 @C 2n species with 2n ≥ 50. DFT, CASPT2 calculations, and MD simulations for several fullerenes of different sizes and symmetries showed that thanks to the formation of strong U(5f 3 )-U(5f 3 ) triple bonds, two U 3+ ions can be incarcerated inside the fullerene. The formation of U−U bonds competes with U−cage interactions that tend to separate the U ions, hindering the observation of short U−U distances in the crystalline structures of diuranium endofullerenes as in U 2 @C 80 . Smaller cages like C 60 exhibit the two interactions, and a strong triple U−U bond with an effective bond order higher than 2 is observed. Although 5f−5f interactions are responsible for the covalent interactions at distances close to 2.5 Å, overlap between 7s6d orbitals is still detected above 4 Å. In general, metal ions within fullerenes should be regarded as templates in cage formation, not as statistically confined units that have little chance of being observed.

show abstract

Recent advances in heterometallic clusters with f-block metal–metal bonds: synthesis, reactivity and applications

Abstract: Recent advances in heterometallic clusters with f-block metal–metal bonds were introduced from the standpoint of synthetic methods, and the corresponding reactivity and applications were also summarized.

Cited by 26 publications

References 76 publications

Highly oxidized U(vi) within the smallest fullerene: gas-phase synthesis and computational study of boron-doped U@C₂₇B

Highly oxidized U(vi) within the smallest fullerene: gas-phase synthesis and computational study of boron-doped U@C₂₇B

Dinitrogen Complexes of Cobalt(−I) Supported by Rare-Earth Metal-Based Metalloligands

Are U–U Bonds Inside Fullerenes Really Unwilling Bonds?

Contact Info

Product

Resources

About

Recent advances in heterometallic clusters with f-block metal–metal bonds: synthesis, reactivity and applications

Abstract: Recent advances in heterometallic clusters with f-block metal–metal bonds were introduced from the standpoint of synthetic methods, and the corresponding reactivity and applications were also summarized.

Cited by 26 publications

References 76 publications

Highly oxidized U(vi) within the smallest fullerene: gas-phase synthesis and computational study of boron-doped U@C27B

Highly oxidized U(vi) within the smallest fullerene: gas-phase synthesis and computational study of boron-doped U@C27B

Dinitrogen Complexes of Cobalt(−I) Supported by Rare-Earth Metal-Based Metalloligands

Are U–U Bonds Inside Fullerenes Really Unwilling Bonds?

Contact Info

Product

Resources

About

Highly oxidized U(vi) within the smallest fullerene: gas-phase synthesis and computational study of boron-doped U@C₂₇B

Highly oxidized U(vi) within the smallest fullerene: gas-phase synthesis and computational study of boron-doped U@C₂₇B