Heterobimetallic-Mediated Dinitrogen Functionalization: N–C Bond Formation at Rhenium-Group 9 Diazenido Complexes

Ouellette, Erik T.; Magdalenski, Julian S.; Bergman, Robert G.; Arnold, John

doi:10.1021/acs.inorgchem.2c02463

Cited by 12 publications

(18 citation statements)

References 59 publications

(77 reference statements)

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“…A related outcome was obtained from Na [523] and [MCl(cod)] 2 [M = Rh (401), Ir (530)] under a nitrogen atmosphere. 370 The products are heterobimetallic complexes [(η 5 -Cp)Re(μ-nacnac)(μ-N 2 )M(η 4 372 For the silicon and germanium analogues, the reaction yielded complexes with short Re−E multiple bonds, as a result of π-interactions with the tetrel atoms. By contrast, the tin derivative has a Re−Sn single bond formed by σ-donation to the Re atom, in a σmetallotetrylene arrangement, and retains its electron lone pair.…”

Section: Monodentate Alkyl Silyl(aryl)amido and Imidomentioning

confidence: 99%

“…Arnold and co-workers have extensively studied the synthesis and reactivity of rhenium metalates featuring β-diketiminato ligands. ,− The anionic Re(I) complex Na[(η 5 -Cp)Re(nacnac)] (Na[ 523 ]; nacnac = N , N′ -bis(2,6-di iso propylphenyl)-3,5-dimethyl-β-diketiminate) displays a rich chemistry which includes, among other reactions, N 2 coordination and trapping and bond formation, as well as serving as a precursor to other metal complexes, including heterometallic compounds. The variety of reactions mediated by 523 is based on its ability to act as a base, nucleophile, or reductant.…”

Section: Synthesis and Basic Reactivity Patterns Of D-block Metalatesmentioning

confidence: 99%

“…The authors demonstrated that the N 2 trapping reactivity is highly dependent on ion pairing interactions since a similar silylation using the ion-separated complex [Na(benzo[12]crown-4) 2 ][ 523 ] afforded only small amounts of product. A related outcome was obtained from Na[ 523 ] and [MCl(cod)] 2 [M = Rh ( 401 ), Ir ( 530 )] under a nitrogen atmosphere . The products are heterobimetallic complexes [(η 5 -Cp)Re(μ-nacnac)(μ-N 2 )M(η 4 -cod)] [M = Rh ( 531 ), Ir ( 532 )] featuring a bridging diazenido ligand end-on coordinated to the rhenium center and the group 9 atom (Scheme ).…”

Section: Synthesis and Basic Reactivity Patterns Of D-block Metalatesmentioning

confidence: 99%

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Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Landaeta,

Horsley Downie,

Wolf

2024

Chem. Rev.

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This review surveys the synthesis and reactivity of low-oxidation state metalate anions of the d-block elements, with an emphasis on contributions reported between 2006 and 2022. Although the field has a long and rich history, the chemistry of transition metalate anions has been greatly enhanced in the last 15 years by the application of advanced concepts in complex synthesis and ligand design. In recent years, the potential of highly reactive metalate complexes in the fields of small molecule activation and homogeneous catalysis has become increasingly evident. Consequently, exciting applications in small molecule activation have been developed, including in catalytic transformations. This article intends to guide the reader through the fascinating world of low-valent transition metalates. The first part of the review describes the synthesis and reactivity of d-block metalates stabilized by an assortment of ligand frameworks, including carbonyls, isocyanides, alkenes and polyarenes, phosphines and phosphorus heterocycles, amides, and redox-active nitrogen-based ligands. Thereby, the reader will be familiarized with the impact of different ligand types on the physical and chemical properties of metalates. In addition, ion-pairing interactions and metal−metal bonding may have a dramatic influence on metalate structures and reactivities. The complex ramifications of these effects are examined in a separate section. The second part of the review is devoted to the reactivity of the metalates toward small inorganic molecules such as H 2 , N 2 , CO, CO 2 , P 4 and related species. It is shown that the use of highly electron-rich and reactive metalates in small molecule activation translates into impressive catalytic properties in the hydrogenation of organic molecules and the reduction of N 2 , CO, and CO 2 . The results discussed in this review illustrate that the potential of transition metalate anions is increasingly being tapped for challenging catalytic processes with relevance to organic synthesis and energy conversion. Therefore, it is hoped that this review will serve as a useful resource to inspire further developments in this dynamic research field.

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Section: Monodentate Alkyl Silyl(aryl)amido and Imidomentioning

confidence: 99%

Section: Synthesis and Basic Reactivity Patterns Of D-block Metalatesmentioning

confidence: 99%

Section: Synthesis and Basic Reactivity Patterns Of D-block Metalatesmentioning

confidence: 99%

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Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Landaeta,

Horsley Downie,

Wolf

2024

Chem. Rev.

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“…The research on N 2 reduction reactions (N 2 RRs) in molecular systems dates back to the 1960s, and ever since seminal work was published by Chatt, Hidai, and co-workers, tremendous efforts have been invested in the development of efficient catalysts for the synthesis of nitrogen-containing molecules directly from N 2 . − Metal dinitrogen complexes necessarily feature strong π-backdonation from electron-rich metal centers to N 2 π* orbitals; therefore, the following N 2 functionalization is almost invariably realized by electrophilic attacks of metal N 2 complexes with potent electrophiles, such as H + , − C + , − and Si + , − leading to diazenido and/or hydrazido complexes (Figure ). More important is that such processes initiate the vast majority of catalytic N 2 RRs .…”

Section: Introductionmentioning

confidence: 99%

Snapshots of Early-Stage Quantitative N₂ Electrophilic Functionalization

Wang

Jiang

et al. 2023

J. Am. Chem. Soc.

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Electrophilic functionalization of N2 moieties in metal dinitrogen complexes typically initiates the catalytic synthesis of N-containing molecules directly from N2. Despite intensive research in the last six decades, how to efficiently and even quantitatively convert N2 into diazenido and hydrazido species still poses a great challenge. In this regard, systematic and comprehensive investigations to elucidate the reaction intricacies are of profound significance. Herein, we report a kinetic dissection on the first and second electrophilic functionalization steps of a new Cr0–N2 system with HOTf, MeOTf, and Me3SiOTf. All reactions pass through fleeting diazenido intermediates and furnish long-lived final hydrazido products, and both steps are quantitative conversions at low temperatures. All of the second-order reaction rates of the first and second transformations were determined as well as the lifetimes of the intervening diazenido species. Based on these findings, we succeeded in large-scale and near-quantitative preparation of all hydrazido species.

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“…The major industrially relevant method for N 2 fixation, known as the Haber-Bosch process, is a highly energy-intensive and environmentally unfriendly process due to the harsh reaction conditions and huge amounts of CO 2 emission . Extensive efforts have been made to develop new molecular systems that can effectively activate or functionalize N 2 under mild conditions to improve our understanding of biological and synthetic N 2 fixation. − Ligand design is an effective method to stabilize metal clusters and regulate the reactivity of the active sites. Although remarkable achievements have been made within the field of N 2 fixation and functionalization, − the mechanistic insights into how the ligands influence the nature of metal centers and promote the reactions remains obscure.…”

mentioning

confidence: 99%

Activation of Dinitrogen Promoted by Adsorption of C₆H₆ on Fe₂VC^– Cluster Anions

Cheng

Jiang

et al. 2023

J. Phys. Chem. Lett.

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The introduction of organic ligands is one of the effective strategies to improve the stability and reactivity of metal clusters. Herein, the enhanced reactivity of benzene-ligated cluster anions Fe 2 VC(C 6 H 6 ) − with respect to naked Fe 2 VC − is identified. Structural characterization suggests that C 6 H 6 is molecularly bound to the dual metal site in Fe 2 VC(C 6 H 6 ) − . Mechanistic details reveal that the cleavage of N�N is feasible in Fe 2 VC(C 6 H 6 ) − /N 2 but hindered by an overall positive barrier in the Fe 2 VC − /N 2 system. Further analysis discloses that the ligated C 6 H 6 regulates the compositions and energy levels of the active orbitals of the metal clusters. More importantly, C 6 H 6 serves as an electron reservoir for the reduction of N 2 to lower the crucial energy barrier of N�N splitting. This work demonstrates that the flexibility of C 6 H 6 in terms of withdrawing and donating electrons is crucial to regulating the electronic structures of the metal cluster and enhancing the reactivity.

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Heterobimetallic-Mediated Dinitrogen Functionalization: N–C Bond Formation at Rhenium-Group 9 Diazenido Complexes

Cited by 12 publications

References 59 publications

Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Snapshots of Early-Stage Quantitative N₂ Electrophilic Functionalization

Activation of Dinitrogen Promoted by Adsorption of C₆H₆ on Fe₂VC^– Cluster Anions

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Heterobimetallic-Mediated Dinitrogen Functionalization: N–C Bond Formation at Rhenium-Group 9 Diazenido Complexes

Cited by 12 publications

References 59 publications

Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Snapshots of Early-Stage Quantitative N2 Electrophilic Functionalization

Activation of Dinitrogen Promoted by Adsorption of C6H6 on Fe2VC– Cluster Anions

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Product

Resources

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Snapshots of Early-Stage Quantitative N₂ Electrophilic Functionalization

Activation of Dinitrogen Promoted by Adsorption of C₆H₆ on Fe₂VC^– Cluster Anions