Understanding the enhanced reactivity of strained intramolecular Frustrated Lewis Pairs DOI Creative Commons
Susana Portela, Israel Fernández

Zeitschrift für anorganische und allgemeine Chemie, Journal Year: 2023, Volume and Issue: 649(6-7)

Published: Jan. 12, 2023

Abstract The poorly understood factors controlling the enhanced reactivity of strained intramolecular frustrated Lewis pairs (FLPs) having a rigid biphenylene tether have been quantitatively explored in detail by means computational methods. With help activation strain model and energy decomposition analysis methods, challenging allene reaction has selected compared to analogous process mediated related FLP more flexible tether, which is significantly less reactive. In addition, influence nature acid atom on considered as well showing that steadily decreases when going down group 13.

Language: Английский

Stronger Together! Mechanistic Investigation into Synergistic Effects during Homogeneous Carbon Dioxide Hydrogenation Using a Heterobimetallic Catalyst DOI
Zeno B. G. Fickenscher, Peter Lönnecke, Anna K. Müller

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(32), P. 12750 - 12761

Published: July 28, 2023

A series of group 6 heterobimetallic complexes [M0;IrIII] (M = Cr, Mo, W) were synthesized and fully characterized, the catalytic behavior was studied. The complex [Mo0;IrIII] (C1) by far most active has shown a considerable synergistic effect, with both metals actively participating in homogeneous carbon dioxide hydrogenation, leading to formate salts. Based on theoretical calculations, interaction is due Pauli repulsion, lowering transition state thus enabling higher activity. mechanism hydrogenation itself studied NMR spectroscopy, kinetic measurements, calculations. nature reaction proven using situ high-pressure (HP) experiments. same experiments also showed that octahedral Mo(CO)3P3 moiety stable under conditions. hydride resting because transfer rate-determining step. This supported HP experiments, calculations contrast monometallic IrIII counterpart C1.

Language: Английский

Citations

4
Computational Insights into SN2 and Proton Transfer Reactions of CH3O− with NH2Y and CH3Y DOI

Huining Feng,

Rui Li, Yang Wu

et al.

ChemPhysChem, Journal Year: 2023, Volume and Issue: 25(1)

Published: Oct. 31, 2023

Abstract Bimolecular nucleophilic substitution (S N 2) reactions have been extensively studied in both theory and experiment. While research on C‐centered S 2 2@C) has ongoing, at neutral nitrogen 2@N) received increased attention recent years. To recommend methods for dynamics simulations, the comparison properties of geometries, vibrational frequencies, energies is done between MP2 six DFT functional calculations experimental data as well high‐level CCSD(T) method CH 3 O − +NH Cl/CH Cl reactions. The relative energy diagrams M06 with Y/NH Y (Y=F, Cl, Br, I) gas solution phase are explored to investigate effects leaving groups, different reaction centers, solvents. We mainly focus computational inv‐S proton transfer (PT) pathways. PT channel more competitive than N‐center reactions, while opposite observed Solvation completely inhibits channel, making dominant pathway. Our study provides new insight into mechanisms rich novel model gas‐phase organic chemistry.

Language: Английский

Citations

4
Modular Divergent Synthesis of Indole Alkaloid Derivatives by an Atypical Ugi Multicomponent Reaction DOI Creative Commons
Brendan Horst,

Niels van Duijnen,

Elwin Janssen

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(29)

Published: March 18, 2024

We present an Ugi multicomponent approach to explore the chemical space around Aspidosperma-type monoterpene indole alkaloids. By variation of isocyanide and carboxylic acid inputs we demonstrate rapid generation molecular diversity possibility introduce handles for further modification. The key three-component reaction showed full diastereoselectivity towards cis-fused ring system, which can be rationalized by DFT calculations that moreover indicate proceeds via a Passerini-type hydrogen bonding mechanism. Several post-Ugi modifications were also performed, including Pictet-Spengler cyclization highly complex nonacyclic natural product hybrid scaffolds.

Language: Английский

Citations

1
Understanding the Reactivity of Diazaborinines towards the Activation of σ‐Bonds DOI Creative Commons
Susana Portela, Israel Fernández

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(33)

Published: April 6, 2023

The poorly understood factors governing the small molecule activation reactions mediated by diazaborinines have been computationally explored in detail using quantum chemical tools. To this end, of E-H σ-bonds (E = H, C, Si, N, P, O, S) has investigated. These reactions, which proceed a concerted manner, are exergonic and, general, associated with relatively low barriers. In addition, barrier becomes lower for bonds involving heavier element same group (ΔG≠ : C>Si; N>P; O>S). This reactivity trend together mode action diazaborinine system quantitatively analyzed means strain model combination energy decomposition analysis method.

Language: Английский

Citations

3
SN2 versus E2 Competition of Cyclic Ethers DOI Creative Commons
Thomas Hansen, Pascal Vermeeren, Kim W. J. Zijderveld

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(50)

Published: June 20, 2023

We have quantum chemically studied the influence of ring strain on competition between two mechanistically different SN 2 and E2 pathways using a series archetypal ethers as substrate in combination with diverse set Lewis bases (F- , Cl- Br- HO- H3 CO- HS- CS- ), relativistic density functional theory at ZORA-OLYP/QZ4P. The is systematically increased going from model acyclic ether to 6- 5- 4- 3-membered ring. found that activation energy pathway sharply decreases when system increased, thus large small cyclic ethers, reactivity increases. In contrast, generally rises along this same series, is, ethers. opposing trends induce mechanistic switch preferred reaction for strong E2, substrates, 2, substrates. Weak are unable overcome higher intrinsic distortivity and, therefore, always favor less distortive reaction.

Language: Английский

Citations

3
Weak Electrostatic Interactions with Bisphosphine Ligands Facilitate Reductive Elimination of PhCF3 from Pd(II) Complexes DOI
Han Gao,

Lingfei Hu,

Yanlei Hu

et al.

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 18(5)

Published: Dec. 30, 2022

The origins of ligand effects on PhCF3 reductive elimination from PdII complexes were computationally investigated by using energy decomposition analysis. results indicate weak electrostatic interactions between ligands and Ph-Pd-CF3 lead to small barriers elimination. Two major factors affecting the are identified.

Language: Английский

Citations

4
Activation of σ‐Bonds by Group 13/Ylide‐Based Ambiphiles: Understanding and Design DOI Creative Commons
Daniel González‐Pinardo, Felix Krämer, Frank Breher

et al.

ChemistryEurope, Journal Year: 2024, Volume and Issue: 2(3-4)

Published: May 1, 2024

Abstract The factors controlling the activation of σ‐bonds promoted by hidden Frustrated Lewis Pairs have been computationally explored using quantum chemical tools. To this end, influence both nature group 13 element acting as acid well cooperative action antagonists on bond was quantitatively analyzed means strain model reactivity in combination with energy decomposition analysis method. It is found that while polar E X −H bonds (E 15 =group element; 16 element) feasible, analogous processes involving non‐polar 14 (CH 4 , SiH or H 2 ) proceed much higher barriers. Nevertheless, these processes, and particular dihydrogen activation, can be realizable (i. e. proceeding a feasible barrier) through rational design.

Language: Английский

Citations

0
η6‐Metalated Aryl Iodides in Diels‐Alder Cycloaddition Reactions: Mode of Activation and Catalysis DOI Creative Commons
Susana Portela, Israel Fernández

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 18(3)

Published: Dec. 14, 2022

The potential application of η6 -metalated aryl iodides as organocatalyst has been explored by means computational methods. It is found that the enhanced halogen bonding donor ability these species, in comparison with their demetalated counterparts, translates into a significant acceleration Diels-Alder cycloaddition reaction involving cyclohexadiene and methyl vinyl ketone. factors behind this acceleration, endo-exo selectivity process influence nature transition metal fragment activity species are quantitatively detail combination Activation Strain Model Energy Decomposition Analysis

Language: Английский

Citations

1
Understanding the enhanced reactivity of strained intramolecular Frustrated Lewis Pairs DOI Creative Commons
Susana Portela, Israel Fernández

Zeitschrift für anorganische und allgemeine Chemie, Journal Year: 2023, Volume and Issue: 649(6-7)

Published: Jan. 12, 2023

Abstract The poorly understood factors controlling the enhanced reactivity of strained intramolecular frustrated Lewis pairs (FLPs) having a rigid biphenylene tether have been quantitatively explored in detail by means computational methods. With help activation strain model and energy decomposition analysis methods, challenging allene reaction has selected compared to analogous process mediated related FLP more flexible tether, which is significantly less reactive. In addition, influence nature acid atom on considered as well showing that steadily decreases when going down group 13.

Language: Английский

Citations

0