Browse
Submit Data
Databases
API
Help

Dataset Information

12 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Gold(I) and Silver(I) π-Complexes with Unsaturated Hydrocarbons.

ABSTRACT: Gold π-complexes have been studied largely in the past 2 decades because of their role in gold-catalyzed reactions. We report an experimental and theoretical investigation of the interaction between a wide range of unsaturated hydrocarbons (alkanes, alkynes, alkadienes, and allenes) and triphenylphosphine-gold(I), triphenylphosphine-silver(I), and acetonitrile-silver(I) cations. The bond dissociation energies of these complexes were determined by mass spectrometry collision-induced dissociations and their structures were studied by density functional theory calculations and infrared photodissociation spectroscopy. The results show that with the same phosphine ligand, gold binds stronger to the π-ligands than silver and thereby activates the unsaturated bond more effectively. Ligand exchange of phosphine by acetonitrile at the silver complexes increases the binding energy as well as the activation of the π-ligands. We also show that the substitution of an unsaturated bond is more important than the bond type.

SUBMITTER: Motloch P

PROVIDER: S-EPMC8155574 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Binding Interactions in Copper, Silver and Gold π-Complexes.

Project description:The copper(I), silver(I), and gold(I) metals bind π-ligands by σ-bonding and π-back bonding interactions. These interactions were investigated using bidentate ancillary ligands with electron donating and withdrawing substituents. The π-ligands span from ethylene to larger terminal and internal alkenes and alkynes. Results of X-ray crystallography, NMR, and IR spectroscopy and gas phase experiments show that the binding energies increase in the order Ag<Cu<Au and the binding energies are slightly higher for alkynes than for alkenes. Modulation of the electron density at the metal using substituents on the ancillary ligands shows that the π-back bonding interaction plays a dominant role for the binding in the copper and gold complexes.

| S-EPMC9305286 | biostudies-literature

Catalytic enantioselective allylation of dienals through the intermediacy of unsaturated pi-allyl complexes.

Project description:The nickel-catalyzed enantioselective addition of allylboronic acid pinacol ester [allylB(pin)] to alpha,beta,gamma,delta-unsaturated aldehydes is described. This reaction results in a remarkable inversion of substrate olefin geometry, providing the Z,E-configured reaction product in good enantioselectivity and olefin stereoselectivity. The reaction appears to proceed by conversion of the dienal to an unsaturated pi-allyl complex followed by reductive elimination via transition state II. Enantioselectivities range from 73-94% ee for a range of delta-substituted dienals when chiral ligand L3 is employed.

| S-EPMC2750882 | biostudies-literature

Increasing reactivity by incorporating π-acceptor ligands into coordinatively unsaturated thiolate-ligated iron(II) complexes.

Project description:Reported herein is the structural, spectroscopic, redox, and reactivity properties of a series of iron complexes containing both a π-donating thiolate, and π-accepting N-heterocycles in the coordination sphere, in which we systematically vary the substituents on the N-heterocycle, the size of the N-heterocycle, and the linker between the imine nitrogen and tertiary amine nitrogen. In contrast to our primary amine/thiolate-ligated Fe(II) complex, [FeII(SMe2N4(tren))]+ (1), the Fe(II) complexes reported herein are intensely colored, allowing us to visually monitor reactivity. Ferrous complexes with R = H substituents in the 6-position of the pyridines, [FeII(SMe2N4(6-H-DPPN)]+ (6) and [FeII(SMe2N4(6-H-DPEN))(MeOH)]+ (8-MeOH) are shown to readily bind neutral ligands, and all of the Fe(II) complexes are shown to bind anionic ligands regardless of steric congestion. This reactivity is in contrast to 1 and is attributed to an increased metal ion Lewis acidity assessed via aniodic redox potentials, Ep,a, caused by the π-acid ligands. Thermodynamic parameters (ΔH, ΔS) for neutral ligand binding were obtained from T-dependent equilibrium constants. All but the most sterically congested complex, [FeII(SMe2N4(6-Me-DPPN)]+ (5), react with O2. In contrast to our Mn(II)-analogues, dioxygen intermediates are not observed. Rates of formation of the final mono oxo-bridged products were assessed via kinetics and shown to be inversely dependent on redox potentials, Ep,a, consistent with a mechanism involving electron transfer.

| S-EPMC8301228 | biostudies-literature

Preferential binding of unsaturated hydrocarbons in aryl-bisimidazolium·cucurbit[8]uril complexes furbishes evidence for small-molecule ?-? interactions.

Project description:Whilst cucurbit[n]urils (CBn) have been utilized in gas encapsulation, only the smaller CBn (n = 5 and 6) have utility given their small cavity size. In this work, we demonstrate that the large cavity of CB8 can be tailored for gaseous and volatile hydrocarbon encapsulation by restricting its internal cavity size with auxiliary aryl-bisimidazolium (Bis, aryl = phenyl, naphthyl, and biphenyl) guests. The binding constants for light hydrocarbons (C ? 4) are similar to those measured with CB6, while larger values are obtained with Bis·CB8 for larger guests. A clear propensity for higher affinities of alkenes relative to alkanes is observed, most pronounced with the largest delocalized naphthalene residue in the auxiliary Bis guest, which provides unique evidence for sizable small-molecule ?-? interactions.

| S-EPMC7006508 | biostudies-literature

Nickel-catalyzed cycloadditions of unsaturated hydrocarbons, aldehydes, and ketones.

Project description:The nickel-catalyzed cycloaddition of unsaturated hydrocarbons and carbonyls is reported. Diynes and enynes were used as coupling partners. Carbonyl substrates include both aldehdyes and ketones. Reactions of diynes and aldehydes afforded the [3,3] electrocyclic ring-opened tautomers, rather than pyrans, in high yields. The cycloaddition reaction of enynes and aldehydes afforded two distinct products. A new carbon-carbon bond is formed, prior to a competitive beta-hydrogen elimination of a nickel alkoxide, between the carbonyl carbon and either one of the carbons of the olefin or the alkyne. The steric hindrance of the enyne greatly affected the chemoselectivity of the cycloaddition of enynes and aldehydes. In some cases, dihydropyran was also formed. The scope of the cycloaddition reaction was expanded to include the coupling of enynes and ketones. No beta-hydrogen elimination was observed in cycloaddition reaction of enynes and ketones. Instead, C-O bond-forming reductive elimination occurred exclusively to afford dihydropyrans in excellent yields. In all cases, complete chemoselectivity was observed; only dihydropyrans where the carbonyl carbon forms a carbon-carbon bond with a carbon of the olefin, rather than of the alkyne, were observed. All cycloaddition reactions occur at room temperature and employ nickel catalysts bearing the hindered 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or its saturated analogue, 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene (SIPr).

| S-EPMC4144363 | biostudies-literature

Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes.

Project description:The hemilabile P^N ligand MeDalphos enables access to a wide range of stable gold(i) π-complexes with unbiased alkenes and alkynes, as well as electron-rich alkenes and for the first time electron-poor ones. All complexes have been characterized by multi-nuclear NMR spectroscopy and whenever possible, by X-ray diffraction analyses. They all adopt a rare tricoordinate environment around gold(i), with chelation of the P^N ligand and side-on coordination of the alkene, including the electron-rich one, 3,4-dihydro-2H-pyrane. The strength of the N → Au coordination varies significantly in the series. It is the way the P^N ligand accommodates the electronic demand at gold, depending on the alkene. Comparatively, when the chelating P^P ligand (ortho-carboranyl)(PPh2)2 is used, gold(i) π-complexes are only isolable with unbiased alkenes. The bonding situation within the gold(i) P^N π-complexes has been thoroughly analyzed by DFT calculations supplemented by Charge Decomposition Analyses (CDA), Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses. Noticeable variations in the donation/back-donation ratio, C[double bond, length as m-dash]C weakening, alkene to gold charge transfer and magnitude of the N → Au coordination were observed. Detailed examination of the descriptors for the Au/alkene interaction and the N → Au coordination actually revealed intimate correlation between the two, with linear response of the MeDalphos ligand to the alkene electronics. The P^N ligand displays non-innocent and adaptative character. The isolated P^N gold(i) π-complexes are reactive and catalytically relevant, as substantiated by the chemo and regio-selective alkylation of indoles.

| S-EPMC8157524 | biostudies-literature

Catalytic Carbochlorocarbonylation of Unsaturated Hydrocarbons via C-COCl Bond Cleavage*.

Project description:Here we report a palladium-catalysed difunctionalisation of unsaturated C-C bonds with acid chlorides. Formally, the C-COCl bond of an acid chloride is cleaved and added, with complete atom economy, across either strained alkenes or a tethered alkyne to generate new acid chlorides. The transformation does not require exogenous carbon monoxide, operates under mild conditions, shows a good functional group tolerance, and gives the isolated products with excellent stereoselectivity. The intermolecular reaction tolerates both aryl- and alkenyl-substituted acid chlorides and is successful when carboxylic acids are transformed to the acid chloride in situ. The reaction also shows an example of temperature-dependent stereodivergence which, together with plausible mechanistic pathways, is investigated by DFT calculations. Moreover, we show that benzofurans can be formed in an intramolecular variant of the reaction. Finally, derivatisation of the products from the intermolecular reaction provides a highly stereoselective approach for the synthesis of tetrasubstituted cyclopentanes.

| S-EPMC8596603 | biostudies-literature

N-heterocyclic carbene gold(I) and silver(I) complexes bearing functional groups for bio-conjugation.

Project description:This work describes several synthetic approaches to append organic functional groups to gold and silver N-heterocyclic carbene (NHC) complexes suitable for applications in biomolecule conjugation. Carboxylate appended NHC ligands (3) lead to unstable Au(I) complexes that convert into bis-NHC species (4). A benzyl protected carboxylate NHC-Au(I) complex 2 was synthesized but deprotection to produce the carboxylic acid functionality could not be achieved. A small library of new alkyne functionalized NHC proligands were synthesized and used for subsequent silver and gold metalation reactions. The alkyne appended NHC gold complex 13 readily reacts with benzyl azide in a copper catalyzed azide-alkyne cycloaddition reaction to form the triazole appended NHC gold complex 14. Cell cytotoxicity studies were performed on DLD-1 (colorectal adenocarcinoma), Hep-G2 (hepatocellular carcinoma), MCF-7 (breast adenocarcinoma), CCRF-CEM (human T-Cell leukemia), and HEK (human embryonic kidney). Complete spectroscopic characterization of the ligands and complexes was achieved using (1)H and (13)C NMR, gHMBC, ESI-MS, and combustion analysis.

| S-EPMC4426189 | biostudies-literature

Dinuclear gold-silver resting states may explain silver effects in gold(I)-catalysis.

Project description:The resting state of the gold(I)-catalyzed hydroarylation of 1 changes in the presence of Ag(+), with silver free catalysts resting at the dinuclear gold structure 5 and Ag(+) containing solutions resting at a heteronuclear species like 6. Adventitious Ag(+) (typically from LAuCl activation) can therefore intercept key organogold intermediates and effect the catalysis even when it does not effect the reaction in Au free control experiments.

| S-EPMC2913295 | biostudies-literature

Syntheses, X-ray crystal structures, and solution behavior of monomeric, cationic, two-coordinate gold(I) pi-alkene complexes.

Project description:Treatment of a suspension of (IPr)AuCl [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine] and AgSbF(6) (1:1) with isobutylene at room temperature for 12 h led to isolation of [(NHC)Au(eta(2)-H(2)C=CMe(2))](+) SbF(6)(-) (1a) in 98% yield, which was characterized by spectroscopy and X-ray crystallography. A number of cationic gold pi-alkene complexes were isolated employing a procedure similar to that used to isolate 1a, two of which were analyzed by X-ray crystallography. Spectroscopy, X-ray crystallography, and alkene binding studies were in accord with a gold-(pi-alkene) interaction dominated by sigma-donation from the alkene to gold.

| S-EPMC2745538 | 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