Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Requirements for Lewis Acid-Mediated Capture and N-N Bond Cleavage of Hydrazine at Iron.

ABSTRACT: An iron complex bearing a pyridine(dicarbene) pincer was designed to probe the requirements of Lewis acid-enabled N2H4 capture and subsequent N-N bond cleavage. Appended boron Lewis acids were installed by two methods to circumvent the incompatibilities associated with Lewis acid/base quenching of free carbenes and boranes. N2H4 capture by borane Lewis acids is dependent on both the Lewis acidity and the steric profile about boron. A substitutionally inert primary coordination sphere at iron prevents an Fe-N2H4 interaction as well as N-N bond homolysis upon reduction.

SUBMITTER: Kiernicki JJ

PROVIDER: S-EPMC6467759 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Requirements for Lewis Acid-Mediated Capture and N-N Bond Cleavage of Hydrazine at Iron.

Kiernicki John J JJ Zeller Matthias M Szymczak Nathaniel K NK

Inorganic chemistry 20190110 2

An iron complex bearing a pyridine(dicarbene) pincer was designed to probe the requirements of Lewis acid-enabled N2H4 capture and subsequent N-N bond cleavage. Appended boron Lewis acids were installed by two methods to circumvent the incompatibilities associated with Lewis acid/base quenching of free carbenes and boranes. N2H4 capture by borane Lewis acids is dependent on both the Lewis acidity and the steric profile about boron. A substitutionally i ...[more]

PMID: 30628782

Similar Datasets

Hydrazine Capture and N-N Bond Cleavage at Iron Enabled by Flexible Appended Lewis Acids.

Project description:Incorporation of two 9-borabicyclo[3.3.1]nonyl substituents within the secondary coordination sphere of a pincer-based Fe(II) complex provides Lewis acidic sites capable of binding 1 or 2 equiv of N2H4. Reduction of the 1:1 Fe:N2H4 species affords a rare Fe(NH2)2 complex in which the amido ligands are stabilized through interactions with the appended boranes. The NH2 units can be released as NH3 upon protonation and exchanged with exogenous N2H4.

| S-EPMC5955611 | biostudies-literature

Tetrahedral iron featuring an appended Lewis acid: distinct pathways for the reduction of hydroxylamine and hydrazine.

Project description:We present the preparation of a nitrogen-based bidentate ligand featuring an appended boron Lewis acid as well as its tetrahedral Fe2+ and Zn2+ complexes. These complexes act as platforms for hydrazine and hydroxylamine capture and reduction chemistry.

| S-EPMC6776999 | biostudies-literature

Molecular fusion of surfactant and Lewis-acid properties for attacking dirt by catalytic bond cleavage.

Project description:The capability of ordinary surfactants in solubilizing hydrophobic compounds can come to a limit, if the extension of a contaminant is too large. An attractive goal is the development of surfactants which can actively reduce the size of dirt. Because strong Lewis acids are known to catalyze both bond formation and cleavage, an integration into the surfactant's molecular framework is tempting. End-group functionalized hepta-dentate ligands, which coordinate to metal ions preventing deactivation by hydrolysis over a broad range of pH values while maintaining strong Lewis-acidity, are herein presented. After proof of amphiphilicity and surfactant characteristics, catalytic properties are investigated for different reactions including the cleavage of proteins. The compounds perform better than benchmark catalysts concerning the attack of unreactive amide bonds. A study with two Sc3+ species as the active site, one non-amphiphilic, the other one being surface-active, underlines the positive effect of surfactant properties for boosting catalytic efficiency.

| S-EPMC7933239 | biostudies-literature

Lewis Base Activation of Lewis Acid: A Detailed Bond Analysis.

Project description:The effect of a Lewis base (LB) on the nucleophilic attack on chalcogeniranium (chalcogen = sulfur and selenium) cations, the so-called LB activation of a Lewis acid, has been studied coupling natural orbital for chemical valence decomposition of the orbital interaction energy with charge displacement analysis. This methodology provides a detailed and accurate description of all the interactions (LB···chalcogen, chalcogen···olefin and olefin···ammonia) present in the system and leads to a deeper understanding of how they influence each other at all stages of the reaction: reactant complex, transition state, and product complex. In particular, the bond between the chalcogen and the olefin has been decomposed in terms of σ donation/π back-donation and the bond components quantified. This allowed determination of a linear relationship between the activation barrier of the nucleophilic attack and the net amount of charge donated by the olefin to the chalcogen.

| S-EPMC6643480 | biostudies-literature

Heterolytic Si-H Bond Cleavage at a Molybdenum-Oxido-Based Lewis Pair.

Project description:The reaction of a molybdenum(VI) oxido imido complex with the strong Lewis acid B(C6 F5 )3 gave access to the Lewis adduct [Mo{OB(C6 F5 )3 }(NtBu)L2 ] featuring reversible B-O bonding in solution. The resulting frustrated Lewis pair (FLP)-like reactivity is reflected by the compound's ability to heterolytically cleave Si-H bonds, leading to a clean formation of the novel cationic MoVI species 3 a (R=Et) and 3 b (R=Ph) of the general formula [Mo(OSiR3 )(NtBu)L2 ][HB(C6 F5 )3 ]. These compounds possess properties highly unusual for molybdenum d0 species such as an intensive, charge-transfer-based color as well as a reversible redox couple at very low potentials, both dependent on the silane used. Single-crystal X-ray diffraction analyses of 2 and 4 b, a derivative of 3 b featuring the [FB(C6 F5 )3 ]- anion, picture the stepwise elongation of the Mo=O bond, leading to a large increase in the electrophilicity of the metal center. The reaction of 3 a and 3 b with benzaldehyde allowed for the regeneration of compound 2 by hydrosilylation of the benzaldehyde. NMR spectroscopy suggested an unusual mechanism for the transformation, involving a substrate insertion in the B-H bond of the borohydride anion.

| S-EPMC6001527 | biostudies-literature

Carbon-fluorine bond cleavage mediated by metalloenzymes.

Project description:Fluorochemicals are a widely distributed class of compounds and have been utilized across a wide range of industries for decades. Given the environmental toxicity and adverse health threats of some fluorochemicals, the development of new methods for their decomposition is significant to public health. However, the carbon-fluorine (C-F) bond is among the most chemically robust bonds; consequently, the degradation of fluorinated hydrocarbons is exceptionally difficult. Here, metalloenzymes that catalyze the cleavage of this chemically challenging bond are reviewed. These enzymes include histidine-ligated heme-dependent dehaloperoxidase and tyrosine hydroxylase, thiolate-ligated heme-dependent cytochrome P450, and four nonheme oxygenases, namely, tetrahydrobiopterin-dependent aromatic amino acid hydroxylase, 2-oxoglutarate-dependent hydroxylase, Rieske dioxygenase, and thiol dioxygenase. While much of the literature regarding the aforementioned enzymes highlights their ability to catalyze C-H bond activation and functionalization, in many cases, the C-F bond cleavage has been shown to occur on fluorinated substrates. A copper-dependent laccase-mediated system representing an unnatural radical defluorination approach is also described. Detailed discussions on the structure-function relationships and catalytic mechanisms provide insights into biocatalytic defluorination, which may inspire drug design considerations and environmental remediation of halogenated contaminants.

| S-EPMC7375919 | biostudies-literature

Lewis acid enhancement by hydrogen-bond donors for asymmetric catalysis.

Project description:Small-molecule dual hydrogen-bond (H-bond) donors such as ureas, thioureas, squaramides, and guanidinium ions enjoy widespread use as effective catalysts for promoting a variety of enantioselective reactions. However, these catalysts are only weakly acidic and therefore require highly reactive electrophilic substrates to be effective. We introduce here a mode of catalytic activity with chiral H-bond donors that enables enantioselective reactions of relatively unreactive electrophiles. Squaramides are shown to interact with silyl triflates by binding the triflate counterion to form a stable, yet highly Lewis acidic, complex. The silyl triflate-chiral squaramide combination promotes the generation of oxocarbenium intermediates from acetal substrates at low temperatures. Enantioselectivity in nucleophile additions to the cationic intermediates is then controlled through a network of noncovalent interactions between the squaramide catalyst and the oxocarbenium triflate.

| S-EPMC5728151 | biostudies-literature

Facile and dynamic cleavage of every iron-sulfide bond in cuboidal iron-sulfur clusters.

Project description:Nature employs weak-field metalloclusters to support a wide range of biological processes. The most ubiquitous metalloclusters are the cuboidal Fe-S clusters, which are comprised of Fe sites with locally high-spin electronic configurations. Such configurations enhance rates of ligand exchange and imbue the clusters with a degree of structural plasticity that is increasingly thought to be functionally relevant. Here, we examine this phenomenon using isotope tracing experiments. Specifically, we demonstrate that synthetic [Fe4S4] and [MoFe3S4] clusters exchange their Fe atoms with Fe2+ ions dissolved in solution, a process that involves the reversible cleavage and reformation of every Fe-S bond in the cluster core. This exchange is facile-in most cases occurring at room temperature on the timescale of minutes-and documented over a range of cluster core oxidation states and terminal ligation patterns. In addition to suggesting a highly dynamic picture of cluster structure, these results provide a method for isotopically labeling pre-formed clusters with spin-active nuclei, such as 57Fe. Such a protocol is demonstrated for the radical S-adenosyl-l-methionine enzyme, RlmN.

| S-EPMC9963086 | biostudies-literature

Borane B-C Bond Cleavage by a Low-Coordinate Iron Hydride Complex and N-N Bond Cleavage by the Hydridoborate Product.

Project description:The iron(II) hydride dimers [L(R)Fe(?-H)(2)FeL(R)] (L(Me) = 2,4-bis(2,6-diisopropylphenylimino) pent-3-yl; L(tBu) = 2,2,6,6-tetramethyl-3,5-bis(2,6-diisopropylphenylimino)hept-4-yl) abstract hydrocarbyl groups from BR'(3) (R' = Et, Ph) to give L(R)FeR' and L(R)Fe(?-H)(2)BR'(2). Mechanistic studies with R = R' = Me are consistent with a process in which the hyride dimer opens one Fe-H bond, and subsequent B-H bond formation is concerted with dissociation of an Fe-H unit. Cleavage of boron-carbon bonds is likely to proceed at least in part from transient quaternary borate anions. In a separate bond-breaking reaction, L(Me)Fe(?-H)(2)BEt(2) reacts with N(2)H(4) to eject H(2) from the bridging hydrides and cleave the N-N bond in the diaminoborate complex L(Me)Fe(?-NH(2))(2)BEt(2). These novel bond-breaking reactions are facilitated by the low coordination number at the iron(II) center.

| S-EPMC2518744 | biostudies-literature

Reversible C-H bond silylation with a neutral silicon Lewis acid.

Project description:The silicon-carbon bond is a valuable linchpin for synthetic transformations. However, installing Si-C functionalities requires metalated C-nucleophiles, activated silicon reagents (silylium ions, silyl radicals, and silyl anions), or transition metal catalysis, and it occurs irreversibly. In contrast, spontaneous C-H silylations with neutral silanes leading to anionic silicates, and their reversible deconstruction, are elusive. Herein, the CH-bond silylation of heterocycles or a terminal alkyne is achieved by reaction with bis(perfluoro(N-phenyl-ortho-amidophenolato))silane and 1,2,2,6,6-pentamethylpiperidine. Computational and experimental insights reveal a frustrated Lewis pair (FLP) mechanism. Adding a silaphilic donor to the ammonium silicate products induces the reformation of the C-H bond, thus complementing previously known irreversible C-H bond silylation protocols. Interestingly, the FLP "activated" N-methylpyrrole exhibits "deactivated" features against electrophiles, while a catalytic functionalization is found to be effective only in the absence of a base.

| S-EPMC10583699 | 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