Unexpected Electronic Behavior of Organic Azide and <scp>Metal‐Carbyne</scp> in Their 1,<scp>3‐Dipolar</scp> Cycloaddition Reaction

Zhang, Jingxuan; Sheong, Fu Kit; Lü, Zhengliang; Zhang, Hong; Lin, Zhenyang

doi:10.1002/cjoc.202000216

Cited by 11 publications

(9 citation statements)

References 39 publications

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“…PISO analysis is an extension of principal interacting orbital (PIO) analysis that can decompose the total interaction between two fragments into pairwise orbital interactions and quantify the magnitude of each orbital interaction by the PIO-based bond index (PBI), 25−27 and very recently, we have successfully applied the PIO analysis to understand the reactivity and regioselectivity of a cycloaddition reaction. 28 The PISO analysis result indeed shows a prominent orbital interaction between the metal d xy orbital and the diene π 3 orbital appearing as the first α/β PISO pair, which is consistent with the aforementioned argument. The second and third α/β PISO pairs stand for donations from diene π 1 and π 2 orbitals to the metal center, and the fourth α/β PISO pair refers to a much weaker backdonation from the metal d xz orbital to the diene π 4 orbital.…”

Section: Resultssupporting

confidence: 85%

“…To better illustrate this feature, we applied our recently developed principal interacting spin orbital (PISO) analysis on this catalytic resting state. PISO analysis is an extension of principal interacting orbital (PIO) analysis that can decompose the total interaction between two fragments into pairwise orbital interactions and quantify the magnitude of each orbital interaction by the PIO-based bond index (PBI), − and very recently, we have successfully applied the PIO analysis to understand the reactivity and regioselectivity of a cycloaddition reaction . The PISO analysis result indeed shows a prominent orbital interaction between the metal d xy orbital and the diene π 3 orbital appearing as the first α/β PISO pair, which is consistent with the aforementioned argument.…”

Section: Resultssupporting

confidence: 75%

“…In this article, we are going to report our DFT calculations and detailed analyses on different electronic state preferences during various steps of the reaction. We have invoked our recently developed principal interacting spin orbital (PISO) analysis to investigate the orbital interactions between the catalyst and the substrates. − We have also made the use of spin natural orbital (SNO) analysis to examine the unpaired electrons of various spin states of the involved species . With the aid of these tools, we have investigated various factors that influence the spin-state preference of each step and explained why two-state reactivity is involved in this reaction.…”

Section: Introductionmentioning

confidence: 99%

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1,4-Selective Hydrovinylation of Diene Catalyzed by an Iron Diimine Catalyst: A Computational Case Study on Two-State Reactivity

Zhang

Sheong

et al. 2020

ACS Catal.

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First-row transition-metal catalysis has been attracting great attention in recent years, partly due to its low toxicity and low cost, as well as a wide variety in reactivities. However, the theoretical understanding behind this important class of reactions is still quite limited, and how the presence of low-lying high-spin states benefits their reactivities is not well known. In this work, we have performed a detailed density functional theory (DFT) study on a previously reported iron diimine-catalyzed hydrovinylation, which we have found to exhibit an interesting "two-state reactivity." Specifically, we found that despite the fact that the resting state of the reaction was experimentally determined to be a triplet state previously, the rate-determining and product-determining steps are found to preferably proceed at a singlet state. A triplet state is better at stabilizing the intermediates and imposes fewer geometric constraints for the substrate to adjust its conformations. A singlet state allows an extra available metal d orbital for interaction with ligand, which facilitates oxidative coupling of diene with an incoming alkene, β-hydride transfer, and ligand substitution. Through in-depth analysis of the electronic structures, we found that the two-state reactivity phenomenon is due to the interplay between orbital interactions, exchange interactions, and coordination geometry, a conclusion that would also serve as an important step in the pursuit of understanding in the first-row transition-metal catalysis and benefit the future design of catalysis with earth-abundant metals.

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Section: Resultssupporting

confidence: 85%

Section: Resultssupporting

confidence: 75%

Section: Introductionmentioning

confidence: 99%

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1,4-Selective Hydrovinylation of Diene Catalyzed by an Iron Diimine Catalyst: A Computational Case Study on Two-State Reactivity

Zhang

Sheong

et al. 2020

ACS Catal.

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“…To dig out the reason for the low reactivity of the Au–B σ-bond and gain a deeper insight into the nature of the Cu/Au–B bond, we performed NBO analysis and our recently developed PIO analysis, which has been shown to be able to clearly delineate the most important orbital interactions between two chemical fragments. The charge distribution/population related to the Cu/Au–B bond in [Cu]–boryl and [Au]–boryl complexes calculated by NBO is summarized in Table .…”

Section: Resultsmentioning

confidence: 99%

Beyond the Nucleophilic Role of Metal–Boryl Complexes in Borylation Reactions

et al. 2021

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Transition metal–boryl complexes play an important role as reactive intermediates in catalytic borylation processes and have enjoyed tremendous exploration. Over the years, it has been well established that a boryl ligand possesses strong nucleophilicity in copper(I)–boryl complexes. Thus, the role played by boron’s “empty” p orbital has often been overlooked and d-electrons’ effect from the metal is even more seldom mentioned, despite the fact that they in theory should also have influence on the reactivity of a metal–boryl complex. In this work, the reactivity of metal–boryl complexes has been systematically studied with the aid of density functional theory calculations. We have revealed that when the metal is more electronegative, the nucleophilic feature of boryl is diminished and will no longer be active, whereas when the boryl is not substituted with π-donating groups, the “empty” p orbital of boron will be active and can serve as the electrophilic site. In addition, when the metal center changes from relatively inert d10 to d8, the d electrons can also play the role of a nucleophile. With a much more comprehensive understanding of metal–boryl complexes, this work will benefit the future catalyst design related to transition-metal-catalyzed borylation reactions.

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“…It can effectively combine complex delocalized interaction patterns into a handful of localized PIOs, thus providing easily interpretable results via the principal component analysis (PCA) [73] . In order to further understand the detailed reaction mechanisms, we carried out PIO analysis on the transition states [74] . The PIO analysis of TS73A (Figure 8a) reveals that the 1 st PIO pair corresponds to a donation from a lone pair on dinitrogen to an empty d orbital of Re with a PBI value of 0.115 and a charge transfer of 0.060 electron, much weaker than the sum of the inverse donation from the d orbital to the two orthogonal anti‐bonding orbitals (π*) of dinitrogen characterized by the 2 nd and 3 rd PIO pairs with PBI values of 0.084, 0.080, respectively.…”

Section: Resultsmentioning

confidence: 99%

Predicting Dinitrogen Activation via Transition‐Metal‐Involved [4+2] Cycloaddition Reaction

Dong

Zhu

2021

Chemistry An Asian Journal

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As the strongest triple bond in nature, the N≡N triple bond activation has always been a challenging project in chemistry. On the other hand, since the award of the Nobel Prize in Chemistry in 1950, the Diels‐Alder reaction has served as a powerful and widely applied tool in the synthesis of natural products and new materials. However, the application of the Diels‐Alder reaction to dinitrogen activation remains less developed. Here we first demonstrate that a transition‐metal‐involved [4+2] Diels‐Alder cycloaddition reaction could be used to activate dinitrogen without an additional reductant by density functional theory calculations. Further study reveals that such a dinitrogen activation by 1‐metalla‐1,3‐dienes screened out from a series of transition metal complexes (38 species) according to the effects of metal center, ligand, and substituents can become favorable both thermodynamically (with an exergonicity of 28.2 kcal mol−1) and kinetically (with an activation energy as low as 13.8 kcal mol−1). Our findings highlight an important application of the Diels‐Alder reaction in dinitrogen activation, inviting experimental chemists’ verification.

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Unexpected Electronic Behavior of Organic Azide and Metal‐Carbyne in Their 1,3‐Dipolar Cycloaddition Reaction

Cited by 11 publications

References 39 publications

1,4-Selective Hydrovinylation of Diene Catalyzed by an Iron Diimine Catalyst: A Computational Case Study on Two-State Reactivity

1,4-Selective Hydrovinylation of Diene Catalyzed by an Iron Diimine Catalyst: A Computational Case Study on Two-State Reactivity

Beyond the Nucleophilic Role of Metal–Boryl Complexes in Borylation Reactions

Predicting Dinitrogen Activation via Transition‐Metal‐Involved [4+2] Cycloaddition Reaction

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