Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Oxidative Addition of Water to Ir(I) Complexes Bearing a Pincer-Type Silyl Ligand.

ABSTRACT: Reaction of water with in situ generated [(PSiP-R)Ir^I] (PSiP-R = [{2-(R₂P)C₆H₄}₂MeSi]^-; R = cyclohexyl, tBu or iPr) from [(PSiP-R)Ir(H)₄] and tert-butylethylene (tbe) showed high ligand dependency. Oxidative addition of water cleanly proceeded in the reaction of [(PSiP-tBu)Ir^I] in THF at room temperature to selectively afford a 16-electron hydrido-hydroxo complex [(PSiP- ^t Bu)Ir(H)(OH)] almost quantitatively. In contrast, the reaction of cyclohexyl and iPr derivatives was unselective and formed various products containing Ir-H bonds. In the case of iPr-derivative, a small amount of 18-electron hydrido-hydroxo aqua complex [(PSiP-iPr)Ir(H)(OH)(H₂O)] was isolated and structurally characterized by X-ray crystallography.

SUBMITTER: Fang H

PROVIDER: S-EPMC9201899 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Direct synthesis of cyanate anion from dinitrogen catalysed by molybdenum complexes bearing pincer-type ligand.

Project description:Dinitrogen is an abundant and promising material for valuable organonitrogen compounds containing carbon-nitrogen bonds. Direct synthetic methods for preparing organonitrogen compounds from dinitrogen as a starting reagent under mild reaction conditions give insight into the sustainable production of valuable organonitrogen compounds with reduced fossil fuel consumption. Here we report the catalytic reaction for the formation of cyanate anion (NCO-) from dinitrogen under ambient reaction conditions. A molybdenum-carbamate complex bearing a pyridine-based 2,6-bis(di-tert-butylphosphinomethyl)pyridine (PNP)-pincer ligand is synthesized from the reaction of a molybdenum-nitride complex with phenyl chloroformate. The conversion between the molybdenum-carbamate complex and the molybdenum-nitride complex under ambient reaction conditions is achieved. The use of samarium diiodide (SmI2) as a reductant promotes the formation of NCO- from the molybdenum-carbamate complex as a key step. As a result, we demonstrate a synthetic cycle for NCO- from dinitrogen mediated by the molybdenum-PNP complexes in two steps. Based on this synthetic cycle, we achieve the catalytic synthesis of NCO- from dinitrogen under ambient reaction conditions.

| S-EPMC9592615 | biostudies-literature

Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand.

Project description:Synthesis and reactivity of iron-dinitrogen complexes have been extensively studied, because the iron atom plays an important role in the industrial and biological nitrogen fixation. As a result, iron-catalyzed reduction of molecular dinitrogen into ammonia has recently been achieved. Here we show that an iron-dinitrogen complex bearing an anionic PNP-pincer ligand works as an effective catalyst towards the catalytic nitrogen fixation, where a mixture of ammonia and hydrazine is produced. In the present reaction system, molecular dinitrogen is catalytically and directly converted into hydrazine by using transition metal-dinitrogen complexes as catalysts. Because hydrazine is considered as a key intermediate in the nitrogen fixation in nitrogenase, the findings described in this paper provide an opportunity to elucidate the reaction mechanism in nitrogenase.

| S-EPMC4961768 | biostudies-literature

Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia.

Project description:It is vital to design effective nitrogen fixation systems that operate under mild conditions, and to this end we recently reported an example of the catalytic formation of ammonia using a dinitrogen-bridged dimolybdenum complex bearing a pincer ligand, where up to twenty three equivalents of ammonia were produced based on the catalyst. Here we study the origin of the catalytic behaviour of the dinitrogen-bridged dimolybdenum complex bearing the pincer ligand with density functional theory calculations, based on stoichiometric and catalytic formation of ammonia from molecular dinitrogen under ambient conditions. Comparison of di- and mono-molybdenum systems shows that the dinitrogen-bridged dimolybdenum core structure plays a critical role in the protonation of the coordinated molecular dinitrogen in the catalytic cycle.

| S-EPMC4015321 | biostudies-literature

Mercury-Free Synthesis of Pincer [C^N^C]AuIII Complexes by an Oxidative Addition/CH Activation Cascade.

Project description:Starting from the commercially available dimethyl sulfide-gold(I) chloride complex (DMSAuCl) and diazonium salts in the presence of 2,6-di-tert-butyl-4-methylpyridine as base, symmetric and unsymmetric [C^N^C]AuIII Cl complexes were synthesized in a selective, photosensitizer-free, photochemical reaction using blue LED light. This new protocol provides the first mercury-free synthesis of these types of pincer-complexes in moderate-to-excellent yields, starting from a readily available gold(I) precursor. Owing to the extraordinary properties of the target compounds, like excellent luminescence and high anticancer activities, the synthesis of such complexes is a highly active field of research, which might make its way to an industrial application. Owing to the disadvantages of the known protocols, especially the toxicity and the selectivity issues in the case of unsymmetric complexes, avoiding the use of mercury, should further accelerate this ongoing development.

| S-EPMC7217051 | biostudies-literature

Environmentally Friendly, Photochemical Access to [ N∧C∧N ]Au<sup>III</sup> Pincer Complexes By Oxidative Addition.

Project description:Starting from commercially available DMSAuCl and diazonium salts, cationic [ N∧C∧N ]AuIII complexes were synthesized in a selective, photosensitizer-free, photochemical reaction by irradiation with blue LED light. This new protocol represents the first easy synthesis of these types of pincer complexes in moderate to excellent yield starting from a readily available gold(I) precursor with nitrogen as the only by-product. Owing to the disadvantages of known protocols, especially the toxicity in the case of a transmetalation with mercury or the necessity for a mostly twofold excess of a gold precursor, this method offers an attractive alternative towards this kind of gold(III) complexes. In addition, the first arylated [ N∧C∧N ]Au(III) pincer complex was synthesized by using this technology.

| S-EPMC8252402 | biostudies-literature

A Ligand Exchange Process for the Diversification of Palladium Oxidative Addition Complexes.

Project description:Palladium oxidative addition complexes (OACs) have recently emerged as useful tools to enable challenging bond connections. However, each OAC can only be formed with one dative ligand at a time. As no one ligand is optimal for every cross-coupling reaction, we herein disclose a ligand exchange protocol for the preparation of a series of OACs bearing a variety of ancillary ligands from one common complex. These complexes were further applied to cross-coupling transformations.

| S-EPMC8437034 | biostudies-literature

Nickel-Alkyl Complexes with a Reactive PNC-Pincer Ligand.

Project description:Based on previous work related to the design and application of rigid tridentate phosphine-pyridine-phenyl coordination offered by a PNC-pincer ligand upon cyclometalation to nickel, the synthesis, spectroscopic and solid state characterization and redox-reactivity of two NiII(PNC) complexes featuring either a methyl (2CH3 ) or CF3 co-ligand (2CF3 ) are described. One-electron oxidation is proposed to furnish C-C reductive elimination, as deduced from a combined chemical, electrochemical, spectroscopic and computational study. One-electron reduction results in a ligand-centered radical anion, as supported by electrochemistry, UV spectroelectrochemistry, EPR spectroscopy, and DFT calculations. This further attenuates the breadth of chemical reactivity offered by such PNC-pincer ligands.

| S-EPMC6001697 | biostudies-literature

Hydrogenation of Terminal Alkenes Catalyzed by Air-Stable Mn(I) Complexes Bearing an N-Heterocyclic Carbene-Based PCP Pincer Ligand.

Project description:Efficient hydrogenations of terminal alkenes with molecular hydrogen catalyzed by well-defined bench stable Mn(I) complexes containing an N-heterocyclic carbene-based PCP pincer ligand are described. These reactions are environmentally benign and atom economic, implementing an inexpensive, earth abundant non-precious metal catalyst. A range of aromatic and aliphatic alkenes were efficiently converted into alkanes in good to excellent yields. The hydrogenation proceeds at 100 °C with catalyst loadings of 0.25-0.5 mol %, 2.5-5 mol % base (KOt Bu) and a hydrogen pressure of 20 bar. Mechanistic insight into the catalytic reaction is provided by means of DFT calculations.

| S-EPMC10952557 | biostudies-literature

Synthesis of Ir<sup>III</sup> Hydrido Complexes by Oxidative Addition of Halogenated Theophylline and Adenine Derivatives.

Project description:The IrIII hydrido complexes [1] and [2] have been synthesized by the regioselective oxidative addition of the N7-H bond of 8-halogenotheophyllines to [IrCl(coe)2]2 in the presence of PPh3. The use of dppf in this reaction yielded the bimetallic IrIII/FeII hydrido complexes [3] and [4]. X-ray diffraction studies confirmed that complexes [1]-[4] feature a theophyllinato ligand coordinated to the metal center in the rarely observed, chelating fashion via the N7 and O1 atoms. In addition, 8-bromoadenine reacts with [IrCl(coe)2]2 in the presence of PPh3 to form the IrIII hydrido complex [5] which features one anionic 8-bromoadeninato and one neutral 8-bromoadenine ligand linked by an intramolecular hydrogen bond. Complex [5] was characterized by high-resolution mass spectrometry and an X-ray diffraction analysis but could not be analyzed by nuclear magnetic resonance spectroscopy because of its low solubility.

| S-EPMC7366355 | biostudies-literature

Electrocatalytic Nitrogen Reduction on a Molybdenum Complex Bearing a PNP Pincer Ligand.

Project description:Electrocatalytic nitrogen reduction (N2R) mediated by well-defined molecular catalysts is poorly developed by comparison with other reductive electrocatalytic transformations. Herein, we explore the viability of electrocatalytic N2R mediated by a molecular Mo-PNP complex. A careful choice of acid, electrode material, and electrolyte mitigates electrode-mediated HER under direct electrolysis and affords up to 11.7 equiv of NH3 (Faradaic efficiency < 43%) at -1.89 V versus Fc+/Fc. The addition of a proton-coupled electron transfer (PCET) mediator has no effect. The data presented are rationalized by an initial electron transfer (ET) that sets the applied bias needed and further reveal an important impact of [Mo] concentration, thereby pointing to potential bimolecular steps (e.g., N2 splitting) as previously proposed during chemically driven N2R catalysis. Finally, facile reductive protonation of [Mo(N)Br(HPNP)] with pyridinium acids is demonstrated.

| S-EPMC10939127 | 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