The treatment of dispersion terms for solution systems

Fang, De‐Cai; Liu, Si‐Cong; Liu, Dan-Yang; Zhu, Xinrui

doi:10.1039/d3cp02733c

Cited by 5 publications

(1 citation statement)

References 52 publications

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“…As a result, the solvent–solute dispersion and solute–solute dispersion should be considered together and shared within this region to establish a new thermal equilibrium. In practice, 1 2 [Δ E D (A···B) + Δ E SSD (A···B)] should be employed to calculate the relative dispersion energy contribution, denoted as B3LYP-D3a + IDSCRF/TZP-DKH(-dfg).…”

Section: Methodsmentioning

confidence: 99%

Theoretical Exploration of Rh/Cu Cooperative Catalysis in C–H Allylation of Benzamide with 1,3-Diene

Yao,

Zhang,

Fang

2024

Organometallics

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Density functional theory has been employed to study the mechanism of the Rh/Cu cooperative catalyzed C−H allylation of benzamide with 1,3-diene. The plausible catalytic cycles encompass C−H activation, diene insertion, oxidative addition for catalyst recovery, and ene reaction for the formation of product. Our calculations conclusively support that the complex between Cp*Rh(OAc)Cl and Cu(OAc) 2 (DMA), denoted as CAT-A, is the most likely active catalyst, facilitating the formation of the Rh(η 3 -allyl) intermediate easily. Following this, the anion [Cu(OAc) 2 (Cl)(DMA)] − , which is dissociated from the Rh coordination site in the first step, returns to the Rh center, providing an OAc group to the Rh coordination center. Subsequently, the Cl atom in [Cu(OAc) 2 (Cl)-(DMA)] − enters the Rh coordination sphere to facilitate catalyst regeneration and separate the precursor of final product 3a. This precursor undergoes an ene reaction with Cu(OAc) 2 (DMA), resulting in the formation of product 3a. We propose a Rh III −Rh IV −Rh III catalytic cycle to elucidate the mechanism governing the titled reaction. Additionally, we explored the subsequent reactions of the generated product 3a and the substituent effects, providing a comprehensive explanation for the experimental observed yields.

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