2022

DOI: 10.1016/j.chempr.2022.03.005

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Selective hydroboration of terminal alkynes catalyzed by heterometallic clusters with uranium–metal triple bonds

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Iskander Douair

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,

³

et al.

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Heterometallic Clusters With Utm Triple Bonds5

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Cited by 19 publications

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“…Fortunately, by the reduction of a mixture of 2 and FeCl 2 with KC 8 , complex 22 with two UFe triple bonds was isolated (Scheme 8). 36 Together with experimental results and DFT calculations, we believe that the four electrons were used to reduce two Fe(II) to two Fe(0) in this process, with the formal oxidation state of U centers remaining at +IV. Complex 22 could be further reduced by 2 equiv of KC 8 , leading to the formation of 23 which features two UFe triple bonds (Scheme 8).…”

Section: Heterometallic Clusters With Utm Triple Bondsmentioning

confidence: 58%

“…Complex 22 could be further reduced by 2 equiv of KC 8 , leading to the formation of 23 which features two UFe triple bonds (Scheme 8). 36 The oxidation state of the Fe centers in 23 is −1, and that of the U centers is +IV. 36 The zero-field 57 Fe Mossbauer spectra of 22 and 23 show single quadrupole doublets (Figure 9).…”

Section: Heterometallic Clusters With Utm Triple Bondsmentioning

confidence: 99%

“…36 The oxidation state of the Fe centers in 23 is −1, and that of the U centers is +IV. 36 The zero-field 57 Fe Mossbauer spectra of 22 and 23 show single quadrupole doublets (Figure 9). The fitting isomer shift (δ) of 22 is 0.68 mm/s (relative to α-Fe at RT), which is slightly larger than that of 23 (δ = 0.55 mm/s).…”

Section: Heterometallic Clusters With Utm Triple Bondsmentioning

confidence: 99%

“…To further extend the UTM triple bond to other TMs, complex 24 with UCo triple bonds was synthesized by the reduction of a mixture of 2 and CoCl 2 with KC 8 (Scheme 9). 36 Complex 25, the intermediate for this process, was isolated by the reaction of 2 with CoCl 2 . Complex 25 could be reduced by KC 8 to generate final product 24.…”

Section: Heterometallic Clusters With Utm Triple Bondsmentioning

confidence: 99%

“…35 The FSR value for this U1−Co1 bond is 0.74, which is slightly larger than those for the The UTM triple bonds in 22−24 were further confirmed by DFT calculations. 36 Bonding UFe molecular orbitals for complex 23 are shown in Figure 12. The interactions of these triple bonds mainly involve the 5f orbital of the U center and the pure d orbitals of the TMs.…”

Section: Heterometallic Clusters With Utm Triple Bondsmentioning

confidence: 99%

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Heterometallic Clusters with Uranium–Metal Bonds Supported by Double-Layer Nitrogen–Phosphorus Ligands

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²

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³

et al. 2022

Acc. Chem. Res.

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Conspectus Heterometallic clusters with M–M bonds have significantly interested chemists because of their attractive structures and synergistic effects in small-molecule activation and catalysis. However, reports of the isolation of heterometallic clusters with uranium–transition metal (U–TM) bonds remain very limited. In this Account, we describe our research in the construction of heterometallic molecular clusters with multiple U–TM single or multiple bonds supported by novel double-layer N–P ligands. Multimetallic synergistic catalysis and small-molecule activation with these species are also summarized. First, according to the hard–soft acid–base theory, we employed a three-armed N–P ligand, which can be used to construct heterometallic clusters with four or six U–Ni bonds. This strategy was also effective in the construction of complexes with direct rare earth metal–TM bonding. The similar two-armed N–P ligands also are effective platforms for the synthesis of heterometallic complexes with U–Ni, U–Pd, and U–Pt bonds. Second, a set of heterometallic clusters featuring URh, UCo, and UFe triple bonds were constructed under routine experimental conditions. X-ray diffraction analysis of these clusters exhibits the shortest U–TM bond distance (1.9693(4) Å for the UFe triple bond) in these complexes. Theoretical studies reveal that the nature of the triple bond is one covalent σ bond and two TM → U dative π bonds. A large Wiberg bond index (WBI) of 2.93 and a significant degree of covalency for the UTM triple bonds were also found in these complexes. Third, these uranium complexes supported by the double-layer N–P ligands exhibit great potential in small-molecule activation. For instance, N2 cleavage without an external reducing agent was achieved by a U(III)–P(III) synergistic six-electron reduction. The synergism between U(III) and P(III) enables the activation of other small molecules, such as O2, P4, and As0 (nano), and highlights the importance of the P atom in the double-layer N−P ligand for the activation of small molecules. A heterometallic cluster with U–Rh bonds can break the strong NN triple bond in N2 in the presence of potassium graphite, suggesting a synergistic effect between U and Rh. This multimetallic synergistic effect was also observed in catalytic processes. A heterometallic cluster with UCo triple bonds shows excellent selectivity and activity in the hydroboration of a series of alkynes under mild conditions. These results lead to effective methods for the construction of heterometallic molecular clusters with U–TM single or multiple bonds and could promote the application of heterometallic clusters with U–TM bonds in catalysis and the activation of small molecules.

“…Fortunately, by the reduction of a mixture of 2 and FeCl 2 with KC 8 , complex 22 with two UFe triple bonds was isolated (Scheme 8). 36 Together with experimental results and DFT calculations, we believe that the four electrons were used to reduce two Fe(II) to two Fe(0) in this process, with the formal oxidation state of U centers remaining at +IV. Complex 22 could be further reduced by 2 equiv of KC 8 , leading to the formation of 23 which features two UFe triple bonds (Scheme 8).…”

Section: Heterometallic Clusters With Utm Triple Bondsmentioning

confidence: 58%

“…Complex 22 could be further reduced by 2 equiv of KC 8 , leading to the formation of 23 which features two UFe triple bonds (Scheme 8). 36 The oxidation state of the Fe centers in 23 is −1, and that of the U centers is +IV. 36 The zero-field 57 Fe Mossbauer spectra of 22 and 23 show single quadrupole doublets (Figure 9).…”

Section: Heterometallic Clusters With Utm Triple Bondsmentioning

confidence: 99%

“…36 The oxidation state of the Fe centers in 23 is −1, and that of the U centers is +IV. 36 The zero-field 57 Fe Mossbauer spectra of 22 and 23 show single quadrupole doublets (Figure 9). The fitting isomer shift (δ) of 22 is 0.68 mm/s (relative to α-Fe at RT), which is slightly larger than that of 23 (δ = 0.55 mm/s).…”

Section: Heterometallic Clusters With Utm Triple Bondsmentioning

confidence: 99%

“…To further extend the UTM triple bond to other TMs, complex 24 with UCo triple bonds was synthesized by the reduction of a mixture of 2 and CoCl 2 with KC 8 (Scheme 9). 36 Complex 25, the intermediate for this process, was isolated by the reaction of 2 with CoCl 2 . Complex 25 could be reduced by KC 8 to generate final product 24.…”

Section: Heterometallic Clusters With Utm Triple Bondsmentioning

confidence: 99%

“…35 The FSR value for this U1−Co1 bond is 0.74, which is slightly larger than those for the The UTM triple bonds in 22−24 were further confirmed by DFT calculations. 36 Bonding UFe molecular orbitals for complex 23 are shown in Figure 12. The interactions of these triple bonds mainly involve the 5f orbital of the U center and the pure d orbitals of the TMs.…”

Section: Heterometallic Clusters With Utm Triple Bondsmentioning

confidence: 99%

See 3 more Smart Citations

Heterometallic Clusters with Uranium–Metal Bonds Supported by Double-Layer Nitrogen–Phosphorus Ligands

¹

,

²

,

³

et al. 2022

Acc. Chem. Res.

Self Cite

View full text Add to dashboard Cite

Conspectus Heterometallic clusters with M–M bonds have significantly interested chemists because of their attractive structures and synergistic effects in small-molecule activation and catalysis. However, reports of the isolation of heterometallic clusters with uranium–transition metal (U–TM) bonds remain very limited. In this Account, we describe our research in the construction of heterometallic molecular clusters with multiple U–TM single or multiple bonds supported by novel double-layer N–P ligands. Multimetallic synergistic catalysis and small-molecule activation with these species are also summarized. First, according to the hard–soft acid–base theory, we employed a three-armed N–P ligand, which can be used to construct heterometallic clusters with four or six U–Ni bonds. This strategy was also effective in the construction of complexes with direct rare earth metal–TM bonding. The similar two-armed N–P ligands also are effective platforms for the synthesis of heterometallic complexes with U–Ni, U–Pd, and U–Pt bonds. Second, a set of heterometallic clusters featuring URh, UCo, and UFe triple bonds were constructed under routine experimental conditions. X-ray diffraction analysis of these clusters exhibits the shortest U–TM bond distance (1.9693(4) Å for the UFe triple bond) in these complexes. Theoretical studies reveal that the nature of the triple bond is one covalent σ bond and two TM → U dative π bonds. A large Wiberg bond index (WBI) of 2.93 and a significant degree of covalency for the UTM triple bonds were also found in these complexes. Third, these uranium complexes supported by the double-layer N–P ligands exhibit great potential in small-molecule activation. For instance, N2 cleavage without an external reducing agent was achieved by a U(III)–P(III) synergistic six-electron reduction. The synergism between U(III) and P(III) enables the activation of other small molecules, such as O2, P4, and As0 (nano), and highlights the importance of the P atom in the double-layer N−P ligand for the activation of small molecules. A heterometallic cluster with U–Rh bonds can break the strong NN triple bond in N2 in the presence of potassium graphite, suggesting a synergistic effect between U and Rh. This multimetallic synergistic effect was also observed in catalytic processes. A heterometallic cluster with UCo triple bonds shows excellent selectivity and activity in the hydroboration of a series of alkynes under mild conditions. These results lead to effective methods for the construction of heterometallic molecular clusters with U–TM single or multiple bonds and could promote the application of heterometallic clusters with U–TM bonds in catalysis and the activation of small molecules.

Complexes Featuring a cis‐[MUM] Core (M=Rh, Ir): A New Route to Uranium‐Metal Multiple Bonds

¹

,

²

,

³

et al. 2023

Angewandte Chemie

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Although examples of multiple bonds between actinide elements and main‐group elements are quite common, studies of the multiple bonds between actinide elements and transition metals are extremely rare owing to difficulties associated with their synthesis. Here we report the first example of molecular uranium complexes featuring a cis‐[M →0false→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M] core (M=Rh, Ir), which exhibits an unprecedented arrangement of two M →0false→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U double dative bond linkages to a single U center. These complexes were prepared by the reactions of chlorine‐bridged heterometallic complexes [{U{N(CH3)(CH2CH2NPiPr2)2}(Cl)2[(μ‐Cl)M(COD)]2}] (M=Rh, Ir) with MeMgBr or MeLi, a new method for the construction of species with U−M multiple bonds. Theoretical calculations including dispersion confirmed the presence of two U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M double dative bonds in these complexes. This study not only enriches the U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M multiple bond chemistry, but also provides a new opportunity to explore the bonding of actinide elements.

Complexes Featuring a cis‐[MUM] Core (M=Rh, Ir): A New Route to Uranium‐Metal Multiple Bonds

¹

,

²

,

³

et al. 2023

Angew Chem Int Ed

Self Cite

View full text Add to dashboard Cite

Although examples of multiple bonds between actinide elements and main‐group elements are quite common, studies of the multiple bonds between actinide elements and transition metals are extremely rare owing to difficulties associated with their synthesis. Here we report the first example of molecular uranium complexes featuring a cis‐[M →0false→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M] core (M=Rh, Ir), which exhibits an unprecedented arrangement of two M →0false→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U double dative bond linkages to a single U center. These complexes were prepared by the reactions of chlorine‐bridged heterometallic complexes [{U{N(CH3)(CH2CH2NPiPr2)2}(Cl)2[(μ‐Cl)M(COD)]2}] (M=Rh, Ir) with MeMgBr or MeLi, a new method for the construction of species with U−M multiple bonds. Theoretical calculations including dispersion confirmed the presence of two U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M double dative bonds in these complexes. This study not only enriches the U ←0false← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M multiple bond chemistry, but also provides a new opportunity to explore the bonding of actinide elements.

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