Browse
Submit Data
Databases
API
Help

Dataset Information

21 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Rh(I)/(III)-N-Heterocyclic Carbene Complexes: Effect of Steric Confinement Upon Immobilization on Regio- and Stereoselectivity in the Hydrosilylation of Alkynes.

ABSTRACT: Rh(I) NHC and Rh(III) Cp* NHC complexes (Cp*=pentamethylcyclopentadienyl, NHC=N-heterocyclic carbene=pyrid-2-ylimidazol-2-ylidene (Py-Im), thiophen-2-ylimidazol-2-ylidene) are presented. Selected catalysts were selectively immobilized inside the mesopores of SBA-15 with average pore diameters of 5.0 and 6.2 nm. Together with their homogenous progenitors, the immobilized catalysts were used in the hydrosilylation of terminal alkynes. For aromatic alkynes, both the neutral and cationic Rh(I) complexes showed excellent reactivity with exclusive formation of the β(E)-isomer. For aliphatic alkynes, however, selectivity of the Rh(I) complexes was low. By contrast, the neutral and cationic Rh(III) Cp* NHC complexes proved to be highly regio- and stereoselective catalysts, allowing for the formation of the thermodynamically less stable β-(Z)-vinylsilane isomers at room temperature. Notably, the SBA-15 immobilized Rh(I) catalysts, in which the pore walls provide an additional confinement, showed excellent β-(Z)-selectivity in the hydrosilylation of aliphatic alkynes, too. Also, in the case of 4-aminophenylacetylene, selective formation of the β(Z)-isomer was observed with a neutral SBA-15 supported Rh(III) Cp* NHC complex but not with its homogenous counterpart. These are the first examples of high β(Z)-selectivity in the hydrosilylation of alkynes by confinement generated upon immobilization inside mesoporous silica.

SUBMITTER: Panyam PKR

PROVIDER: S-EPMC9299010 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Regioselective allene hydrosilylation catalyzed by N-heterocyclic carbene complexes of nickel and palladium.

Project description:Regioselective methods for allene hydrosilylation have been developed, with regioselectivity being governed primarily by the choice of metal. Alkenylsilanes are produced via nickel catalysis with larger N-heterocyclic carbene (NHC) ligands, and allylsilanes are produced via palladium catalysis with smaller NHC ligands. These complementary methods allow either regioisomeric product to be obtained with exceptional regiocontrol.

| S-EPMC3838997 | biostudies-literature

Ligand steric contours to understand the effects of N-heterocyclic carbene ligands on the reversal of regioselectivity in Ni-catalyzed reductive couplings of alkynes and aldehydes.

Project description:The regioselectivities of N-heterocyclic carbene (NHC) ligands in Ni-catalyzed alkyne-aldehyde reductive coupling reactions with silane reducing agents are investigated using density functional theory. Reversal of regioselectivity can be achieved by varying the steric bulkiness of the ligand. The steric influences of NHC ligands are highly anisotropic. Regioselectivity is primarily controlled by the steric hindrance at the region of the ligand close to the alkyne. Analysis of 2D contour maps of the NHC ligands indicates that the regioselectivities are directly affected by the shape and orientation of the N-substituents on the ligand.

| S-EPMC3128454 | biostudies-literature

Steric and Electronic Effects in Gold N-Heterocyclic Carbene Complexes Revealed by Computational Analysis.

Project description:A computational analysis of a series of cationic and neutral gold imidazolylidene and benzimidizolylidene complexes is reported. The Bond Dissociation Energies of the various ligands in the complexes calculated at the PBE0-D3/def2-TZVP level of theory increase with increasing ligand volume, except for those of complexes containing t-butyl-substituted ligands, which are anomalously low particularly for the benzimidazolylidene species. Atoms in Molecules studies show the presence of a variety of weak intramolecular interactions, characterised by the presence of bond critical points with a range of different properties. Energy Decomposition Analysis and calculation of Electrostatic Surface Potentials indicate that some interactions are weakly attractive dispersion-type interactions, while others are repulsive. The octanol/water partition coefficients (log P values) were calculated as a measure of the lipophilicities of the complexes and were found to increase with increasing volume.

| S-EPMC6488199 | biostudies-literature

Mercury(II) Complexes of Anionic N-Heterocyclic Carbene Ligands: Steric Effects of the Backbone Substituent.

Project description:Mercury(II) complexes (Me-maloNHCDipp)HgCl (1b), (t-Bu-maloNHCDipp)HgCl (2b) and (t-Bu-maloNHCDipp)HgMe (2c) supported by anionic N-heterocyclic carbenes have been obtained in good yields from the reaction of the potassium salt of N-heterocyclic carbene ligand precursors and mercury(II) salts, HgCl2 and MeHgI. These molecules have been characterized by 1H-NMR, 13C-NMR and IR spectroscopy and elemental analysis. X-ray crystal structures of 1b and 2b are also presented. Interestingly, complex 1b is polymeric {(Me-maloNHCDipp)HgCl}n in the solid state, as a result of inter-molecular Hg-O contacts, and features rare three coordinate mercury sites with a T-shaped arrangement, whereas the (t-Bu-maloNHCDipp)HgCl (2b) is monomeric and has a linear, two-coordinate mercury center. The formation of T-shaped structure and the aggregation of complex 1b is attributable to the reduced steric demand of the N-heterocyclic carbene ligand backbone substituent.

| S-EPMC7464600 | biostudies-literature

Supramolecular Immobilization of Adamantyl and Carboxylate Modified N-Heterocyclic Carbene Ligand on Cucurbituril Substrates.

Project description:Herein, the design, synthesis, supramolecular interactions and structural analysis of a novel bidentate carboxylate chelating N-heterocylic carbene (NHC) ligand is presented. The NHC structure was modified to strategically incorporate adamantyl moiety for the formation of a supramolecular complex with host molecules such as cucurbiturils. The adamantyl modified NHC ligand could potentially be used in recoverable homogeneous catalysts when Immobilized on a solid support via host-guest chemistry. As a versatile precursor, NHC ligand (8) was synthesized and characterized by 1H-NMR, 13C-NMR, FTIR, single crystal x-ray crystallography and elemental analysis. A proof-of-principle non-covalent immobilization of the NHC ligand (8) with a Cucurbit[7]uril (CB7) host was demonstrated using 1H-NMR titration.

| S-EPMC8911794 | biostudies-literature

Sterically Demanding AgI and CuI N-Heterocyclic Carbene Complexes: Synthesis, Structures, Steric Parameters, and Catalytic Activity.

Project description:The synthesis and full characterization of new air-stable AgI and CuI complexes bearing structurally bulky expanded-ring N-heterocyclic carbene (erNHC) ligands is presented. The condensation of protonated NHC salts with Ag2 O afforded a collection of AgI complexes, and their first use as ligand transfer reagents led to novel isostructural CuI or AuI complexes. In situ deprotonation of the NHC salts in the presence of a copper(I) source, provides a library of new CuI complexes. The solid-state structures feature large N-CNHC -N angles (118-128°) and almost identical angles between the aryl groups on the nitrogen atoms and the plane of the N-C-N unit of the carbene (i.e. torsion angles close to 0°). Among the steric parameters, the percent buried volume (%Vbur ) values span easily in the 50-57 % range, and that one of (9-Dipp)CuBr complex (%Vbur =57.5) overcomes to other known erNHC-metal complexes reported to date. Preliminary catalytic experiments in the copper-catalyzed coupling between N-tosylhydrazone and phenylacetylene, afforded 76-93 % product at the 0.5-2.5 mol % catalyst loading, proving the stability of CuI erNHC complexes at elevated temperatures (100 °C).

| S-EPMC7216994 | biostudies-literature

Steric and Electronic Effects in N-Heterocyclic Carbene Gold(III) Complexes: An Experimental and Computational Study.

Project description:A series of neutral acridine-based gold(III)-NHC complexes containing the pentafluorophenyl (-C6F5) group were synthesized. All of the complexes were fully characterized by analytical techniques. The square planar geometry around the gold center was confirmed by X-ray diffraction analysis for complexes 1 (Trichloro [1-methyl-3-(9-acridine)imidazol-2-ylidene]gold(III)) and 2 (Chloro-bis(pentafluorophenyl)[1-methyl-3-(9-acridine)imidazol-2-ylidene]gold(III)). In both cases, the acridine rings play a key role in the crystal packing of the solid structures by mean of π-π stacking interactions, with centroid-centroid and interplanar distances being similar to those found in other previously reported acridine-based Au(I)-NHC complexes. A different reactivity when using a bulkier N-heterocyclic carbene ligand such as 1,3-bis-(2,6-diisopropylphenyl)-2-imidazolidinylidene (SIPr) was observed. While the use of the acridine-based NHC ligand led to the expected organometallic gold(III) species, the steric hindrance of the bulky SIPr ligand led to the formation of the corresponding imidazolinium cation stabilized by the tetrakis(pentafluorophenyl)aurate(III) [Au(C6F5)4]- anion. Computational experiments were carried out in order to figure out the ground state electronic structure and the binding formation energy of the complexes and, therefore, to explain the observed reactivity.

| S-EPMC9740751 | biostudies-literature

Regio- and enantioselective umpolung gem-difluoroallylation of hydrazones via palladium catalysis enabled by N-heterocyclic carbene ligand.

Project description:The enantioselective construction of C-CF2R (R: alkyl or fluoroalkyl) bonds has attracted the attention of synthetic chemists because of the importance of chiral fluorinated compounds in life and materials sciences. Catalytic asymmetric fluoroalkylation has mainly been realized under organocatalysis and Lewis acid catalysis, with substrates limited to carbonyl compounds. Few examples using transition-metal catalysis exist, owing to side reactions including decomposition and isomerization of fluoroalkylating reagents. Herein we report umpolung asymmetric difluoroallylation of hydrazones with 3-bromo-3,3-difluoropropene (BDFP) under palladium catalysis. Difluoroallylation products having quaternary chiral carbon centers are afforded in good yields with high α/γ- and enantioselectivities. The usefulness of the reaction products is demonstrated and an inner-sphere mechanism of the reaction is proposed. The use of chiral N-heterocyclic carbene as ligand is the key for the selectivities as well as the productivity of the reaction.

| S-EPMC8589859 | biostudies-literature

Regio- and Enantioselective <i>N</i>-Heterocyclic Carbene-Catalyzed Annulation of Aminoindoles Initiated by Friedel-Crafts Alkylation.

Project description:Chiral indoles annulated on the benzene ring are unique and significant in natural and medicinal compounds. However, accessing these enantioenriched molecules has often been overlooked. The present study introduces an organocatalytic protocol to access these compounds efficiently, demonstrated by substrate scope, functional group tolerance, and using only 1 mol % of a chiral conjugated acid catalyst. Additionally, the study explores regioselectivity, gram-scale reactions, and follow-up transformations, underscoring the method's potential.

| S-EPMC11348421 | biostudies-literature

Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism.

Project description:The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of ?-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a (syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. Mechanistic studies by both experiments and density functional theory (DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism-nucleophilic attack of enolate oxygen on Palladium followed by C-C bond-forming [3,3']-reductive elimination.

| S-EPMC4906412 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data