Dinitrogen Functionalization Affording Structurally Well-Defined Cobalt Diazenido Complexes

Zhong, Ming; Cui, Xianlu; Wu, Botao; Wang, Gao‐Xiang; Zhang, Wen‐Xiong; Wei, Junnian; Zhao, Lili; Xi, Zhenfeng

doi:10.31635/ccschem.021.202100945

Cited by 14 publications

(10 citation statements)

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“…The product was identified to be a silylated S8). More importantly, its spectroscopic features 45,46 3i and S80), and significant red shifts 48 of ν N−N by at least 200 cm −1 in the IR spectra (Figures S18−S26). TD-DFT calculations predicted that the low-lying excitation of 3-Me appears at 608 nm, which matches the experiment (630 nm) very well (Figure 3a).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Following this route of reasoning, [Cp*(depe)Cr II –NN–Si i Pr 3 ] ( 3-Si i Pr 3 ) bearing a more bulky Si i Pr 3 substituent could be independently accessed with an isolated yield of 88% by a combination of 1 with i Pr 3 SiCl at 193 K. Single-crystal X-ray crystallography analyses demonstrated that the molecular structure of 3-Si i Pr 3 features a lengthened N–N (1.224(2) Å) and a shortened Cr–N α (1.7061(15) Å) bond (Figure ) relative to those measured for 1-crypt (N–N: 1.156(3) and 1.160(3) Å; Cr–N α : 1.7955(19) and 1.788(2) Å) (Table S8). More importantly, its spectroscopic features , (δ( 15 N) = 390.83 and 222.07 ppm; ν N–N = 1611 cm –1 , ν N–N = 1553 cm –1 for 15 N-labeled 3-Si i Pr 3 - 15 N 2 ) (Figures h, S11, and S12) closely resemble those of 3-Me and 3-SiMe 3 , which supports our assignments of 3-Me and 3-SiMe 3 as diazenido species.…”

Section: Resultsmentioning

confidence: 99%

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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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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Snapshots of Early-Stage Quantitative N₂ Electrophilic Functionalization

Wang

Jiang

et al. 2023

J. Am. Chem. Soc.

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“…555 Nitrogen functionalization has been achieved at cobalt complexes with chelating phosphine ligands. 556,557 In 2019, Miller and Long described Co(−I)-dinitrogen complexes featuring two examples of the triphos family of tripodal ligands, specifically N-triphos and C-triphos. 556 547,548,558 848 and 849 coordinate dinitrogen between the cobalt centers and the stabilizing Mg 2+ cation in an end-on bridging fashion.…”

Section: General Comments On N 2 Activation By Metalate Complexes The...mentioning

confidence: 99%

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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“…[ 10‐13 ] Hence, a variety of strategies have been developed to achieve dinitrogen reduction more efficiently and in an environmentally‐friendly manner. [ 14‐37 ]…”

Section: Introductionmentioning

confidence: 99%

Light‐Driven Dinitrogen Activation with Transition Metal Complexes: Mechanisms and Applications^†

Zhao

Wei

2023

Chin. J. Chem.

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Comprehensive SummaryThe Haber‐Bosch process, which is used for ammonia (NH3) synthesis, requires vast amounts of energy, accounting for approximately 1%—2% of the world's annual energy consumption. Therefore, researchers in both industry and academia are interested in developing sustainable and environmentally friendly methods for synthesizing nitrogenous compounds at ambient conditions using renewable energy sources such as visible light. While several examples of thermal activation of dinitrogen molecules have been demonstrated using various transition metals and ligand frameworks, the use of light to weaken or split the strong N—N bond has been less explored. This article presents an overview of molecular complexes capable of dinitrogen photocleavage and provides mechanistic insights into the photoactivation process through experimental and theoretical studies. We believe this review will provide readers with an in‐depth understanding of the current state‐of‐the‐art and future research perspectives, particularly in the use of visible light for dinitrogen activation and transformation.

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Dinitrogen Functionalization Affording Structurally Well-Defined Cobalt Diazenido Complexes

Cited by 14 publications

References 65 publications

Snapshots of Early-Stage Quantitative N₂ Electrophilic Functionalization

Snapshots of Early-Stage Quantitative N₂ Electrophilic Functionalization

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

Light‐Driven Dinitrogen Activation with Transition Metal Complexes: Mechanisms and Applications^†

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Dinitrogen Functionalization Affording Structurally Well-Defined Cobalt Diazenido Complexes

Cited by 14 publications

References 65 publications

Snapshots of Early-Stage Quantitative N2 Electrophilic Functionalization

Snapshots of Early-Stage Quantitative N2 Electrophilic Functionalization

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

Light‐Driven Dinitrogen Activation with Transition Metal Complexes: Mechanisms and Applications†

Contact Info

Product

Resources

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Snapshots of Early-Stage Quantitative N₂ Electrophilic Functionalization

Snapshots of Early-Stage Quantitative N₂ Electrophilic Functionalization

Light‐Driven Dinitrogen Activation with Transition Metal Complexes: Mechanisms and Applications^†