Browse
Submit Data
Databases
API
Help

Dataset Information

30 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A cyclic disilylated stannylene: synthesis, dimerization, and adduct formation.

ABSTRACT: Reaction of 1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane with [(Me(3)Si)(2)N](2)Sn led to the formation of an endocyclic distannene via the dimerization of a transient stannylene. In the presence of strong donor molecules such as PEt(3), the stannylene could be trapped as adduct. Reaction of the PEt(3) derivative with B(C(6)F(5))(3) gave rise to the formation of the stannylene B(C(6)F(5))(3) adduct.

SUBMITTER: Arp H

PROVIDER: S-EPMC3144678 | biostudies-literature | 2011 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

A cyclic disilylated stannylene: synthesis, dimerization, and adduct formation.

Arp Henning H Baumgartner Judith J Marschner Christoph C Müller Thomas T

Journal of the American Chemical Society 20110325 15

Reaction of 1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane with [(Me(3)Si)(2)N](2)Sn led to the formation of an endocyclic distannene via the dimerization of a transient stannylene. In the presence of strong donor molecules such as PEt(3), the stannylene could be trapped as adduct. Reaction of the PEt(3) derivative with B(C(6)F(5))(3) gave rise to the formation of the stannylene B(C(6)F(5))(3) adduct. ...[more]

PMID: 21438553

Similar Datasets

Dispersion energy enforced dimerization of a cyclic disilylated plumbylene.

Project description:By reaction of 1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane with PbBr(2) in the presence of triethylphosphine a base adduct of a cyclic disilylated plumbylene could be obtained. Phosphine abstraction with B(C(6)F(5))(3) led to formation of a base-free plumbylene dimer, which features an unexpected single donor-acceptor PbPb bond. The results of density functional computations at the M06-2X and B3LYP level of theory indicate that the dominating interactions which hold the plumbylene subunits together and which define its actual molecular structure are attracting van der Waals forces between the two large and polarizable plumbylene subunits.

| S-EPMC3336735 | biostudies-literature

Cyclic Disilylated and Digermylated Germylenes.

Project description:The preparation of triethylphosphine adducts of cyclic disilylated or digermylated germylenes was achieved by reaction of 1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane with GeBr2·(dioxane) and PEt3. Phosphine abstraction with B(C6F5)3 allowed formation of the base-free germylenes, which undergo 1,2-trimethylsilyl shifts to the germylene atom to form the respective silagermene or digermene, which further dimerize in [2 + 2] cycloadditions to tricyclic compounds. The reasons responsible for the germylenes' completely different reactivities in comparison to the previously studied analogous stannylenes and plumbylenes were elucidated in a theoretical study.

| S-EPMC3714166 | biostudies-literature

Coordination chemistry of disilylated stannylenes with group 10 d10 transition metals: silastannene vs stannylene complexation.

Project description:The coordination behavior of disilylated stannylenes toward zerovalent group 10 transition metal complexes was studied. This was accomplished by reactions of PEt3 adducts of disilylated stannylenes with zerovalent group 10 transition metal complexes. The thus obtained products differed between the first row example nickel and its heavier congeners. While with nickel stannylene complex formation was observed, coordination of the stannylenes to palladium and platinum compounds led to unusual silastannene complexes of these metals. A computational model study indicated that in each case metal stannylene complexes were formed first and that the disilylstannylene/silastannene rearrangement occurs only after complexation to the group 10 metal. The isomerization is a two-step process with relatively small barriers, suggesting a thermodynamic control of product formation. In addition, the results of the computational investigation revealed a subtle balance of steric and electronic effects, which determines the relative stability of the metalastannylene complex relative to its silastannene isomer. In the case of cyclic disilylstannylenes, the Pd(0) and Pt(0) silastannene complexes are found to be more stable, while with acyclic disilylstannylenes the Ni(0) stannylene complex is formed preferentially.

| S-EPMC3670429 | biostudies-literature

Basic Reactivity Pattern of a Cyclic Disilylated Germylene.

Project description:In order to estimate the reactivity of disilylated germylene phosphine adducts, a cyclic version of this compound class was reacted with a number of different reagents. Reactions with the chalcogens sulfur, selenium, and tellurium led to dimers of the heavy ketone analogues. Reactions with water and ethyl bromide proceeded to give the respective oxidized germanol and germyl bromide. Two different reactions with alkynes were observed which led either to a germacyclopropene, by addition of tolane to the germylene, or to a silagermacyclobutene, likely formed by addition of the alkyne across a silagermene. Reaction via the silagermene was also observed in the reaction with benzophenone. Reaction of a germylene phosphine adduct with GeCl2·(dioxane) provided insertion of the silylated germylene into a Ge-Cl bond, leading to a germylated chlorogermylene phosphine adduct.

| S-EPMC4997532 | biostudies-literature

Coordination chemistry of cyclic disilylated stannylenes and plumbylenes to group 4 metallocenes.

Project description:Reduction of group 4 metallocene dichlorides with magnesium in the presence of cyclic disilylated stannylene or plumbylene phosphine adducts yielded the respective metallocene tetrylene phosphine complexes. Under the same conditions the use of the respective dimerized stannylene or plumbylene gave metallocene ditetrylene complexes. A computational analysis of these reactions revealed for all investigated compounds multiple-bonded character for the M-E(II) linkage, which can be rationalized in the case of the monotetrylene complex with the classical ?-donor/?-acceptor interaction. The strength of the M-E(II) bond increases descending group 4 and decreases going from Sn to its heavier congener Pb. The weakness of the Ti-E(II) bonds is caused by the significantly reduced ability of the titanium atom for d-p ?-back-bonding.

| S-EPMC3396127 | biostudies-literature

Coordination Chemistry of Cyclic Disilylated Germylenes and Stannylenes with Group 11 Metals.

Project description:Reactions of Et3P adducts of bissilylated germylenes and stannylenes with gold, silver, and copper cyanides led to cyanogermyl or -stannyl complexes of the respective metals. In the course of the reaction the phosphine moved to the metal, while the cyanide migrated to the low-coordinate group 14 element. The respective gold complexes were found to be monomeric, whereas the silver and copper complexes exhibited a tendency to dimerize in the solid state. Attempts to abstract the phosphine ligand with B(C6F5)3 led only to the formation of adducts with the borane coordinating to the cyanide nitrogen atom.

| S-EPMC4276716 | biostudies-literature

Nickel-Catalyzed Intramolecular C-O Bond Formation: Synthesis of Cyclic Enol Ethers.

Project description:An efficient and exceptionally mild intramolecular nickel-catalyzed carbon-oxygen bond-forming reaction between vinyl halides and primary, secondary, and tertiary alcohols has been achieved. Zinc powder was found to be an essential additive for obtaining high catalyst turnover and yields. This operationally simple method allows direct access to cyclic vinyl ethers in high yields in a single step.

| S-EPMC4985346 | biostudies-literature

An indenide-tethered N-heterocyclic stannylene.

Project description:The structure of (μ-1κN:2(η2),κ2 N,N'-(2-{[2,6-bis(propan-2-yl)phen-yl]aza-nid-yl}eth-yl)[2-(1H-inden-1-yl)eth-yl]aza-nido)(1,4,7,10,13,16-hexa-oxa-cyclo-octa-dec-ane-1κ6 O)lithiumtin, [LiSn(C8H16O4)(C25H31N2)], at 100 K has monoclinic (P21/n) symmetry. Analysis of the coordination of the Sn to the indenyl ring shows that the Sn inter-acts in an η2 fashion. A database survey showed that whilst this coordination mode is unusual for Ge and Pb compounds, Sn displays a wider range of coordination modes to cyclo-penta-dienyl ligands and their derivatives.

| S-EPMC7001827 | biostudies-literature

Adduct Formation of Delamanid with NAD in Mycobacteria.

Project description:Delamanid (DLM), a nitro-dihydroimidazooxazole derivative currently approved for pulmonary multidrug-resistant tuberculosis (TB) therapy, is a prodrug activated by mycobacterial 7,8-didemethyl-8-hydroxy 5-deazaflavin electron transfer coenzyme (F420)-dependent nitroreductase (Ddn). Despite inhibiting the biosynthesis of a subclass of mycolic acids, the active DLM metabolite remained unknown. Comparative liquid chromatography-mass spectrometry (LC-MS) analysis of DLM metabolites revealed covalent binding of reduced DLM with a nicotinamide ring of NAD derivatives (oxidized form) in DLM-treated Mycobacterium tuberculosis var. Bacille de Calmette et Guérin. Isoniazid-resistant mutations in the type II NADH dehydrogenase gene (ndh) showed a higher intracellular NADH/NAD ratio and cross-resistance to DLM, which were restored by complementation of the mutants with wild-type ndh Our data demonstrated for the first time the adduct formation of reduced DLM with NAD in mycobacterial cells and its importance in the action of DLM.

| S-EPMC7179590 | biostudies-literature

Combined computational and experimental studies on cysteine-sulfadiazine adduct formation.

Project description:The electrochemical characterization of sulfadiazine-cysteine (SD-CYS) adduct formation was performed in phosphate buffer (pH 7) on the basis of voltammetric current and peak potential measurements. Due to the association of cysteine with sulfadiazine, the reduction peak currents of mercuric and mercurous cysteine thiolates decreased and their peak potentials simultaneously shifted to less negative potentials. By using the current changes of mercurous cysteine thiolate, it was determined that cysteine and sulfadiazine are associated with a 1:1 stoichiometry with a conditional association constant of 1.99 ×104 M-1 . In addition to experimental studies, a computational approach was carried out to study the geometrical parameters, electron densities, and UV-Vis absorption spectra of sulfadiazine and SDCYS adduct in water. Calculated (B3LYP/6-311++G(d,p) level) and experimental UV-Vis absorption spectra of the compounds were found to be in good agreement in water. The computational study suggests that cysteine bound to the C(5) on the pyrimidine ring via SH-group nucleophilic attack. Computational results reveal that sulfadiazine and its derivatives effectively bind cysteine and may lead to new molecules/drugs to target cysteine.

| S-EPMC7671221 | 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