Heterometallic Clusters with Multiple Rare Earth Metal–Transition Metal Bonding

Shi, Kaiying; Douair, Iskander; Feng, Genfeng; Wang, Penglong; Zhao, Yue; Maron, Laurent; Zhu, Congqing

doi:10.1021/jacs.1c01771

Cited by 24 publications

(30 citation statements)

References 73 publications

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“…of [IrCl(COD)] 2 following the same procedure, and was isolated as orange crystals in 74% yield. The formation of complexes 2a and 2b is analogous to the frustrated Lewis pair reactivity observed previously in rare-earth organometallic chemistry 50 – 52 . Both 2a and 2b were characterized by nuclear magnetic resonance (NMR) spectroscopy (Supplementary Figs.…”

Section: Resultssupporting

confidence: 72%

Photochemical Synthesis of Transition Metal-Stabilized Uranium(VI) Nitride Complexes

et al. 2022

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Uranium nitrides play important roles in dinitrogen activation and functionalization and in chemistry for nuclear fuels, but the synthesis and isolation of the highly reactive uranium(VI) nitrides remains challenging. Here, we report an example of transition metal (TM) stabilized U(VI) nitride complexes, which are generated by the photolysis of azide-bridged U(IV)-TM (TM = Rh, Ir) precursors. The U(V) nitride intermediates with bridged azide ligands are isolated successfully by careful control of the irradiation time, suggesting that the photolysis of azide-bridged U(IV)-TM precursors is a stepwise process. The presence of two U(VI) nitrides stabilized by three TMs is clearly demonstrated by an X-ray crystallographic study. These TM stabilized U(V) nitride intermediates and U(VI) nitride products exhibit excellent stability both in the solid-state and in THF solution under ambient light. Density functional theory calculations show that the photolysis necessary to break the N-N bond of the azide ligands implies excitation from uranium f-orbital to the lowest unoccupied molecular orbital (LUMO), as suggested by the strong antibonding N-(N2) character present in the latter.

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Section: Resultssupporting

confidence: 72%

Photochemical Synthesis of Transition Metal-Stabilized Uranium(VI) Nitride Complexes

et al. 2022

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“…The As a proof of concept, a series of heterometallic clusters with rare earth (RE) metal−metal bonds were also constructed using this N−P platform. 23 As shown in Scheme 3, complexes 6 were first synthesized by the reaction of 1 with RE[N(SiMe 3 ) 2 ] 3 (RE = La, Ce, Nd). Treating 6 with 3 equiv of [Rh(COD)Cl] 2 afforded 7, in which the RE metals and the Rh are attached to Cl atoms (Figure 4).…”

Section: Heterometallic Clusters With U−tm Singlementioning

confidence: 99%

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

et al. 2022

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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.

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“…However, such systems with LM → Ln bonds remain rare, probably due to the large and hard Ln 3+ ions associated with highly oxo-, halo-, and nitrophilic nature, which have posed synthetic challenges to heterobimetallic complexes containing LM–Ln bonds . Only a few examples of unsupported polar LM–Ln bonds (LM = Re, Fe, Ru) were known . Recent studies largely focused on phosphinomethylamido and phosphinoamido ligands to support LM → Ln dative bonds and applications in catalytic alkene and alkyne hydrogenations …”

Section: Introductionmentioning

confidence: 99%

Three-Coordinate Pd(0) with Rare-Earth Metalloligands: Synergetic CO Activation and Double P–C Bond Cleavage-Formation Reactions

Cui

et al. 2021

Inorg. Chem.

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Metalation of β-diketiminato rare-earth metal complexes L nacnac Ln(PhNCH 2 PPh 2 ) 2 (Ln = Y, Yb, Lu) with (COD)Pd(CH 2 SiMe 3 ) 2 afforded three-coordinate Pd(0) complexes supported by two sterically less bulky phosphines and a Pd → Ln dative interaction. The Pd(0) center is prone to ligation with isonitrile and CO; in the latter case, the insertion of a second CO with the Y−N bond was assisted via a precoordination of CO on the Pd(0) center, which led to the formation of an anionic Pd(0) carbamoyl. The reaction of the Pd−Y complex with iodobenzene showed a remarkable double P−C bond cleavage-formation pathway within the heterobimetallic Pd−Y core to afford (Ph 3 P) 2 PdI(Ph), imine PhNCH 2 , and a β-diketiminato yttrium diiodide. In the related reaction of L nacnac Y(PhNCH 2 PPh 2 ) 2 with (Ph 3 P) 2 PdI(Ph), the P−C bond cleavage following with a N−C bond formation was observed. Computational studies revealed a synergetic bimetallic mechanism for these reactions.

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Heterometallic Clusters with Multiple Rare Earth Metal–Transition Metal Bonding

Cited by 24 publications

References 73 publications

Photochemical Synthesis of Transition Metal-Stabilized Uranium(VI) Nitride Complexes

Photochemical Synthesis of Transition Metal-Stabilized Uranium(VI) Nitride Complexes

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

Three-Coordinate Pd(0) with Rare-Earth Metalloligands: Synergetic CO Activation and Double P–C Bond Cleavage-Formation Reactions

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