Browse
Submit Data
Databases
API
Help

Dataset Information

7 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Competition for Hydride Between Silicon and Boron: Synthesis and Characterization of a Hydroborane-Stabilized Silylium Ion.

ABSTRACT: Potent main-group Lewis acids are capable of activating element-hydrogen bonds. To probe the rivalry for hydride between silylium- and borenium-ion centers, a neutral precursor with the hydrosilane and hydroborane units in close proximity on a naphthalene-1,8-diyl platform was designed. Abstraction of one hydride leads to a hydroborane-stabilized silylium ion rather than a hydrosilane-coordinated borenium ion paired with [B(C₆ F₅ )₄ ]^- or [HCB₁₁ Cl₁₁ ]^- as counteranions. Characterization by multinuclear NMR spectroscopy and X-ray diffraction supported by DFT calculations reveals a cationic, unsymmetrical open three-center, two-electron (3c2e) Si-H-B linkage.

SUBMITTER: Gao H

PROVIDER: S-EPMC9303568 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Synthesis of a Counteranion-Stabilized Bis(silylium) Ion.

Project description:The preparation of a molecule with two alkyl-tethered silylium-ion sites from the corresponding bis(hydrosilanes) by two-fold hydride abstraction is reported. The length of the conformationally flexible alkyl bridge is crucial as otherwise the hydride abstraction stops at the stage of a cyclic bissilylated hydronium ion. With an ethylene tether, the open form of the hydronium-ion intermediate is energetically accessible and engages in another hydride abstraction. The resulting bis(silylium) ion has been NMR spectroscopically and structurally characterized. Related systems based on rigid naphthalen-n,m-diyl platforms can only be converted into the dications when the positively charged silylium-ion units are remote from each other (1,8 versus 1,5 and 2,6).

| S-EPMC7317492 | biostudies-literature

Subphthalocyaninato Boron(III) Hydride: Synthesis, Structure and Reactivity.

Project description:Subphthalocyanine (SubPc) chemistry has been limited so far by their high sensitivity toward strong nucleophiles. In particular, the substitution of the axial chlorine atom by a nucleophilic group in the case of less-reactive SubPcs, such as those bearing electron-withdrawing peripheral substituents, presents some limitations and requires harsh conditions. By taking advantage of the electrophilic character of DIBAL-H, it has been possible to prepare for the first time SubPc-hydride derivatives that exhibit high reactivity as hydroboration reagents of aldehydes. This hydride transfer requires using a typical carbonyl activator (trimethylsilyl triflate) and only one equivalent of aldehyde, affording SubPcs with an axial benzyloxy group in good yield. This transformation has proven to be a useful alternative method for the axial functionalisation of dodecafluoroSubPc, a paradigmatic SubPc derivative, by using electrophiles for the first time. Considering the increasing interest in SubPcs as electron-acceptor semiconductors with remarkable absorption in the visible range to replace fullerene in organic photovoltaic (OPV) devices, it is of the utmost importance to develop new synthetic methodologies for their axial functionalisation.

| S-EPMC8456786 | biostudies-literature

Facile Access to Stable Silylium Ions Stabilized by N-Heterocyclic Imines.

Project description:Novel silylium ions with N-heterocyclic imines were successfully synthesized. The reaction of trimethylsilyl imidazolin-2-imine Me?SiNIPr (NIPr = bis(2,6-diisopropylphenyl)-imidazolin-2-imino) with B(C?F?)? leads to dimeric imino-substituted silylium ions through a methyl group abstraction on the silicon atom. Meanwhile, the intermolecular imino-coordinated silylium ion is formed by using the less sterically crowded imine Me?SiNItBu (NItBu = bis(tert-butyl)-imidazolin-2-imino). Furthermore, the treatment of dimethylchlorosilane Me?(Cl)SiNIPr with AgOTf affords the contact ion pair Me?(OTf)SiNIPr by substitution of the chloride. A novel complex with the formula [Me?(DMAP)SiNIPr][OTf] was prepared by coordination with 4-dimethylamino-pyridine (DMAP). In the solid state, the DMAP adduct [Me?(DMAP)SiNIPr][OTf] contains a distinct [Me?(DMAP)SiNIPr]? moiety.

| S-EPMC6273809 | biostudies-other

Essential role of hydride ion in ruthenium-based ammonia synthesis catalysts.

Project description:The efficient reduction of atmospheric nitrogen to ammonia under low pressure and temperature conditions has been a challenge in meeting the rapidly increasing demand for fertilizers and hydrogen storage. Here, we report that Ca2N:e-, a two-dimensional electride, combined with ruthenium nanoparticles (Ru/Ca2N:e-) exhibits efficient and stable catalytic activity down to 200 °C. This catalytic performance is due to [Ca2N]+·e1-x-H x- formed by a reversible reaction of an anionic electron with hydrogen (Ca2N:e- + xH ? [Ca2N]+·e1-x-H x-) during ammonia synthesis. The simplest hydride, CaH2, with Ru also exhibits catalytic performance comparable to Ru/Ca2N:e-. The resultant electrons in these hydrides have a low work function of 2.3 eV, which facilitates the cleavage of N2 molecules. The smooth reversible exchangeability between anionic electrons and H- ions in hydrides at low temperatures suppresses hydrogen poisoning of the Ru surfaces. The present work demonstrates the high potential of metal hydrides as efficient promoters for low-temperature ammonia synthesis.

| S-EPMC6013784 | biostudies-literature

Sterically Stabilized Terminal Hydride of a Diiron Dithiolate.

Project description:The kinetically robust hydride [t-HFe2(Me2pdt)(CO)2(dppv)2]+ ([t-H1]+) (Me2pdt2- = Me2C(CH2S-)2; dppv = cis-1,2-C2H2(PPh2)2) and related derivatives were prepared with 57Fe enrichment for characterization by NMR, FT-IR, and NRVS. The experimental results were rationalized using DFT molecular modeling and spectral simulations. The spectroscopic analysis was aimed at supporting assignments of Fe-H vibrational spectra as they relate to recent measurements on [FeFe]-hydrogenase enzymes. The combination of bulky Me2pdt2- and dppv ligands stabilizes the terminal hydride with respect to its isomerization to the 5-16 kcal/mol more stable bridging hydride ([?-H1]+) with t1/2(313.3 K) = 19.3 min. In agreement with the nOe experiments, the calculations predict that one methyl group in [t-H1]+ interacts with the hydride with a computed CH···HFe distance of 1.7 Å. Although [t-H571]+ exhibits multiple NRVS features in the 720-800 cm-1 region containing the bending Fe-H modes, the deuterated [t-D571]+ sample exhibits a unique Fe-D/CO band at ?600 cm-1. In contrast, the NRVS spectra for [?-H571]+ exhibit weaker bands near 670-700 cm-1 produced by the Fe-H-Fe wagging modes coupled to Me2pdt2- and dppv motions.

| S-EPMC5821139 | biostudies-literature

Synthesis and structures of anionic rhenium polyhydride complexes of boron-hydride ligands and their application in catalysis.

Project description:The rhenium complex, [K(DME)(18-c-6)][ReH4(Bpin)(η2-HBpin)(κ2-H2Bpin)] 1, comprising hydride and boron ligands only, has been synthesized by exhaustive deoxygenation of the commercially available perrhenate anion (ReO4 -) with pinacol borane (HBpin). The structure of 1 was analysed by X-ray crystallography, NMR spectroscopy, and DFT calculations. While no hydrides were located in the X-ray crystal structure, it revealed a trigonal arrangement of pinacol boron ligands. Variable-temperature NMR spectroscopy supported the presence of seven hydride ligands but further insight was hindered by the fluxionality of both hydride and boron ligands at low temperature. Further evaluation of the structure by Ab Initio Random Structure Searching (AIRSS) identified the presence of hydride, boryl, σ-borane, and dihydroborate ligands. This complex, either isolated or prepared in situ, is a catalyst for the 1,4-hydroboration of N-heteroaromatic substrates under simple operating procedures. It also acts as a reagent for the stoichiometric C-H borylation of toluene, displaying high meta regioselectivity in the borylated products. Reaction of 1 with 9-BBN resulted in HBpin substitution to form the new anionic tetra(dihydroborate) complex [K(DME)(18-c-6)][Re(κ2-H-9-BBN)4] 4 for which the hydride positions were clearly identified by X-ray crystallography. The method used to generate these isolable yet reactive boron-hydride complexes is direct and straightforward and has potential utility for the exploitation of other metal oxo compounds in operationally simple catalytic reactions.

| S-EPMC8162066 | biostudies-literature

(Dimesityl)boron Benzodithiophenes: Synthesis, Electrochemical, Photophysical and Theoretical Characterization.

Project description:Triarylboranes containing linear or angular benzodithiophene moieties and bearing one or two dimesitylboron units were synthesized. The electrochemical and optical features of these compounds were investigated by cyclic voltammetry, UV/Vis and fluorescence spectroscopy while DFT calculations were run to analyze the energetic landscape of these systems. For both linear and angular benzodithiophenes, symmetrical disubstitution leads to the highest photoluminescence yields. The linear benzodithiophene disubstituted with two dimesitylboron units proved to be the most interesting and promising molecule as an electron-transport material for organic electronics owing to its LUMO energy level of -2.84 eV which is close to those of commonly used electron transport materials like bathocuproine or bathophenantroline.

| S-EPMC8780079 | biostudies-literature

Synthesis of Quaternary Carbon Stereogenic Centers by Diastereoselective Conjugate Addition of Boron-Stabilized Allylic Nucleophiles to Enones.

Project description:A method for the site-selective and diastereoselective conjugate addition of boron-stabilized allylic nucleophiles to α,β-unsaturated ketones is disclosed. Transformations involve easily prepared γ,γ-disubstituted allyldiboron reagents and proceed in the presence of a fluoride activator at 80 °C. Reactions proceed with a wide variety of enones and allyldiboron reagents efficiently to deliver ketone products that contain otherwise difficult-to-access vicinal β-tertiary and γ-quaternary carbon stereogenic centers and an alkenylboron moiety. The utility of the method is highlighted by several transformations, including cross-coupling and carbocyclizations.

| S-EPMC7289652 | biostudies-literature

Rapid Microwave Synthesis, Characterization and Reactivity of Lithium Nitride Hydride, Li?NH.

Project description:Lithium nitride hydride, Li?NH, was synthesised from lithium nitride and lithium hydride over minute timescales, using microwave synthesis methods in the solid state for the first time. The structure of the microwave-synthesised powders was confirmed by powder X-ray diffraction [tetragonal space group I4?/a; a = 4.8864(1) Å, c = 9.9183(2) Å] and the nitride hydride reacts with moist air under ambient conditions to produce lithium hydroxide and subsequently lithium carbonate. Li?NH undergoes no dehydrogenation or decomposition [under Ar(g)] below 773 K. A tetragonal-cubic phase transition, however, occurs for the compound at ca. 770 K. The new high temperature (HT) phase adopts an anti-fluorite structure (space group Fm 3? m; a = 4.9462(3) Å) with N3- and H- ions disordered on the 4a sites. Thermal treatment of Li?NH under nitrogen yields a stoichiometric mixture of lithium nitride and lithium imide (Li?N and Li?NH respectively).

| S-EPMC5452770 | biostudies-literature

Heterogeneous reduction of carbon dioxide by hydride-terminated silicon nanocrystals.

Project description:Silicon constitutes 28% of the earth's mass. Its high abundance, lack of toxicity and low cost coupled with its electrical and optical properties, make silicon unique among the semiconductors for converting sunlight into electricity. In the quest for semiconductors that can make chemicals and fuels from sunlight and carbon dioxide, unfortunately the best performers are invariably made from rare and expensive elements. Here we report the observation that hydride-terminated silicon nanocrystals with average diameter 3.5 nm, denoted ncSi:H, can function as a single component heterogeneous reducing agent for converting gaseous carbon dioxide selectively to carbon monoxide, at a rate of hundreds of μmol h(-1) g(-1). The large surface area, broadband visible to near infrared light harvesting and reducing power of SiH surface sites of ncSi:H, together play key roles in this conversion. Making use of the reducing power of nanostructured hydrides towards gaseous carbon dioxide is a conceptually distinct and commercially interesting strategy for making fuels directly from sunlight.

| S-EPMC4996982 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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