Theoretical Study on N-N Activation by Thiolate-bridged Dinuclear Dinitrogen Transition-metal Complexes

Zhang, Yiwe; Ma, Xiaojing; Zhang, Xin; Lei, Ming

doi:10.6023/a15120781

Cited by 3 publications

(2 citation statements)

References 14 publications

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“…金属酰肼是固氮酶催化二氮还原成氨的中间体, 对与肼配合物反应的化学研究有助于阐明过渡金属辅助氮还原的细节 [79][80][81][82][83] . 迄今为止, 已经对过渡金属配合物与肼或取代肼的反应进行了广泛的研究, 以阐明 N-N 键是如何被过渡金属配合物裂解的.…”

Section: 化学学报unclassified

Trinuclear Transition Metal Complexes in Catalytic Reactions

Ma¹,

Li²,

Lei³

2023

Acta Chimica Sinica

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Polynuclear transition metal complexes are widely used as homogeneous catalysts, and the polymetallic active sites of enzymes also play an important role in the mechanism of biochemical reactions under ambient conditions. As the efficient polymetallic catalysts for the activation of small molecules, trinuclear metal complexes have been attracted extensive attention. In order to understand the role of trinuclear transition metal complexes in catalytic reactions, we have classified the trinuclear transition metal complexes according to metal centers, and summarized the characteristics of their ligands, as well as their catalytic applications. Based on the metal centers, the geometric structure and electronic characteristics of the complexes are discussed. Based on the peripheral ligands, the characteristics of the coordination environment, which enable the aggregation of three independent metal sites, are highlighted. In terms of catalytic applications of trinuclear transition metal complexes, the catalytic mechanisms involving specific chemical bonds activation are focused on. Finally, we outlook the crucial potential application in this emerging field.

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Section: 化学学报unclassified

Trinuclear Transition Metal Complexes in Catalytic Reactions

Ma¹,

Li²,

Lei³

2023

Acta Chimica Sinica

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“…In addition, we have calculated single-point energy data using ωB97X-D/BSII//ωB97X-D/BSI (BSII denotes LanL2DZ for the Pd center and 6-311+G** for other atomes) on the basis of stationary points along the favorable reaction pathways. The hybrid density functional method ωB97X-D is reliable and was used in previous work . The transition states (TSs) were further confirmed by vibrational analyses and characterized only by imaginary frequencies.…”

Section: Computational Detailsmentioning

confidence: 99%

DFT Study on the Mechanism of Tandem Oxidative Acetoxylation/Ortho C–H Activation/Carbocyclization Catalyzed by Pd(OAc)₂

Zhang

et al. 2016

Organometallics

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A density functional theory (DFT) study has been conducted to unveil the mechanisms of tandem oxidative acetoxylation/ortho C−H activation/ carbocyclization catalyzed by Pd(OAc) 2 . The potential competitive reaction pathways between oxidative acetoxylation and ortho C−H activation, C−H activation with outer-sphere and inner-sphere acetate ligands, and the role of DMSO in the reaction have been discussed in detail. The calculated results indicate that the oxidative acetoxylation proceeds before ortho C−H activation in this tandem reaction in a neutral system without DMSO as a ligand coordinated to Pd. A six-membered transition state is proposed in the oxidative acetoxylation step, and a six-membered transition state is proposed in the palladium carboxylate catalyzed sp 2 C−H activation step. The coordination of outer-sphere acetate ion to Pd decreases the energy barrier of the step of ortho sp 2 C−H activation. In addition, this theoretical work demonstrates that the cosolvent DMSO as a ligand coordinated with Pd decreases the energy barrier of C−H activation. Also, the reaction tandem sequence changes to ortho C−H activation/oxidative acetoxylation/carbocyclization induced by DMSO as a ligand coordinated with Pd.

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A Mononuclear Iron Thiolate Complex with N-Heterocyclic Carbene Ligation

Li¹,

Ouyang²,

Zou³

et al. 2022

Acta Chimica Sinica

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Theoretical Study on N-N Activation by Thiolate-bridged Dinuclear Dinitrogen Transition-metal Complexes

Cited by 3 publications

References 14 publications

Trinuclear Transition Metal Complexes in Catalytic Reactions

Trinuclear Transition Metal Complexes in Catalytic Reactions

DFT Study on the Mechanism of Tandem Oxidative Acetoxylation/Ortho C–H Activation/Carbocyclization Catalyzed by Pd(OAc)₂

A Mononuclear Iron Thiolate Complex with N-Heterocyclic Carbene Ligation

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Theoretical Study on N-N Activation by Thiolate-bridged Dinuclear Dinitrogen Transition-metal Complexes

Cited by 3 publications

References 14 publications

Trinuclear Transition Metal Complexes in Catalytic Reactions

Trinuclear Transition Metal Complexes in Catalytic Reactions

DFT Study on the Mechanism of Tandem Oxidative Acetoxylation/Ortho C–H Activation/Carbocyclization Catalyzed by Pd(OAc)2

A Mononuclear Iron Thiolate Complex with N-Heterocyclic Carbene Ligation

Contact Info

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Resources

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DFT Study on the Mechanism of Tandem Oxidative Acetoxylation/Ortho C–H Activation/Carbocyclization Catalyzed by Pd(OAc)₂