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| http://dx.doi.org/10.1002/anie.201202137 | DOI Listing |
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Correlation Between NMR Coupling Constants and σ-Donating Properties of N-Heterocyclic Carbenes and Their Derivatives.
Chemistry
January 2025
LCM, Ecole polytechnique, CNRS, IP Paris, 91128, Palaiseau, France.
Is the J coupling constant for protonated carbene a relevant measure of its σ-donation ability? This paper addresses this question by comparing calculated J values with various experimental and theoretical approaches across a broad spectrum of carbene compounds. We examined Arduengo-type NHCs based on the 2-imidazolylidene scaffold and many other derivatives with modified frameworks, including carbenes with extended, saturated, or conjugated rings, reduced heteroatom stabilization, alternative heteroatoms, permanently charged carbenes, acyclic carbenes, amidocarbenes, and cyclic amino(alkyl/aryl) carbenes, carbodicarbenes and carbodiphosphoranes. Our findings reveal a nuanced relationship between different parameters associated with σ-interaction, such as J, Huynh electronic parameter (HEP), σ-donation from ETS-NOCV, and lone pair energy.
View Article and Find Full Text PDFGreen-Light Hydrosilylation Photocatalysis with Platinum(II)Metalla-N-Heterocyclic Carbene Complexes.
Chemistry
November 2024
Saint Petersburg State University, 7/9 Universitetskaya Nab., St. Petersburg, 199034, Russian Federation.
Platinum(II) metalla-N-heterocyclic carbene complexes featuring pyridyl heterocyclic moiety demonstrate remarkable catalytic efficiency in alkyne hydrosilylation under green light irradiation. The photocatalytic properties of complexes are rationalised by the photo-induced charge transfer occurring in extended condensed system identified with the help of various experimental (UV/vis and emission spectroscopy, cyclic voltammetry) and theoretical methods (DFT/TD-DFT, IFCT analysis).
View Article and Find Full Text PDFPlatinum(II)-Substituted Phenylacetylide Complexes Supported by Acyclic Diaminocarbene Ligands.
Inorg Chem
June 2022
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Room 112, Houston, Texas 77204-5003, United States.
We introduce phosphorescent platinum aryl acetylide complexes supported by -butyl-isocyanide and strongly σ-donating acyclic diaminocarbene (ADC) ligands. The precursor complexes -[Pt(CNBu)(C≡CAr)] () are treated with diethylamine, which undergoes nucleophilic addition with one of the isocyanides to form the -[Pt(CNBu)(ADC)(C≡CAr)] complexes (). The new compounds incorporate either electron-donating groups (4-OMe and 4-NMe) or electron-withdrawing groups [3,5-(OMe), 3,5-(CF), 4-CN, and 4-NO] on the aryl acetylide.
View Article and Find Full Text PDFTheoretical Study on Reaction Mechanisms of Dinitrogen Activation and Coupling by Carbene-Stabilized Borylenes in Comparison with Intramolecular C-H Bond Activation.
Chem Asian J
June 2022
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, 361005 Xiamen, P. R. China.
Dinitrogen (N ) activation is particularly challenging due to the significantly strong N≡N bond, let alone the catenation of two N molecules. Recent experimental study shows that cyclic (alkyl)(amino)carbene (CAAC)-stabilized borylenes are able to tackle N activation and coupling below room temperature. Here we carry out density functional theory calculations to explore the corresponding reaction mechanisms.
View Article and Find Full Text PDFComprehensive Basicity Scales for N-Heterocyclic Carbenes in DMSO: Implications on the Stabilities of N-Heterocyclic Carbene and CO Adducts.
Chem Asian J
January 2020
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
A very broad acidity scale (≈40 pK units) for about 400 N-heterocyclic carbene precursors (NHCPs) with various backbones and electronic features, including imidazolylidenes, 1,2,4-triazolylidenes, cyclic diaminocarbenes (CDACs), diamidocarbenes (DACs), thiazolylidenes, cyclic (alkyl)(amino)carbenes (CAACs) and mesoionic carbenes (MICs), was established in DMSO by a well examined computational method. Varying the backbone structure or flanking N-substituents can have different extent of acidifying effects, depending on both the nature and number of substituent(s). The Gibbs energies (ΔG s) for the reactions between the corresponding NHCs and CO were also calculated.
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