Search results for "bond cleavage"
showing 10 items of 58 documents
Light-Induced Alkylation of (Hetero)aromatic Nitriles in a Transition-Metal-Free C–C-Bond Metathesis
2017
A light-induced C–C-σ-bond metathesis was achieved through transition-metal-free activation of an unstrained C(sp3)–C(sp3)-σ-bond in 1-benzyl-1,2,3,4-tetrahydroisoquinolines. A photoredox-mediated single-electron oxidation of these precursor amines yield radical cations which undergo a homolytic cleavage of a C(sp3)–C(sp3)-σ-bond rather than the well-known α-C–H-scission. The resulting carbon-centered radicals are used in the ipso-substitution of (hetero)aromatic nitriles proceeding through another single-electron transfer-mediated C–C-bond cleavage and formation.
Reversible O–H bond activation by an intramolecular frustrated Lewis pair
2019
The interactions of the O-H bonds in alcohols, water and phenol with dimethylxanthene-derived frustrated Lewis pairs (FLPs) have been probed. Within the constraints of this backbone framework, the preference for adduct formation or O-H bond cleavage to give the corresponding zwitterion is largely determined by pKa considerations. In the case of the PPh2/B(C6F5)2 system and p-tBuC6H4OH, an equilibrium is established between the two isomeric forms which allows the thermodynamic parameters associated with zwitterion formation via O-H bond cleavage to be probed.
Carbon monoxide activation by a molecular aluminium imide: C-O bond cleavage and C-C bond formation
2020
Anionic molecular imide complexes of aluminium are accessible via a rational synthetic approach involving the reactions of organo azides with a potassium aluminyl reagent. In the case of K2 [(NON)Al(NDipp)]2 (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene; Dipp=2,6-diisopropylphenyl) structural characterization by X-ray crystallography reveals a short Al-N distance, which is thought primarily to be due to the low coordinate nature of the nitrogen centre. The Al-N unit is highly polar, and capable of the activation of relatively inert chemical bonds, such as those found in dihydrogen and carbon monoxide. In the case of CO, uptake of two molecules of the substrate…
DFT Study on the Interaction of Tris(benzene-1,2-dithiolato)molybdenum Complex with Water. A Hydrolysis Mechanism Involving a Feasible Seven-Coordina…
2016
In the present work, the reactivity of the tris(benzene-1,2-dithiolato)molybdenum complex ([Mo(bdt)3]) toward water is studied by means of the density functional theory (DFT). DFT calculations were performed using the M06, B3P86, and B3PW91 hybrid functionals for comparison purposes. The M06 method was employed to elucidate the reaction pathway, relative stability of the intermediate products, nature of the Mo–S bond cleavage, and electronic structure of the involved molybdenum species. This functional was also used to study the transference of electrons from the molybdenum center toward the ligands. The reaction pathway confirms that [Mo(bdt)3] undergoes hydrolysis, yielding dihydroxo-bis(…
Molecular Mechanism of the site-specific self-cleavage of the RNA phosphodiester backbone by a Twister Ribozyme
2017
Published as part of the special collection of articles derived from the 10th Congress on Electronic Structure: Principles and Applications (ESPA-2016). The catalytic activity of some classes of natural RNA, named as ribozymes, has been discovered just in the past decades. In this paper, the cleavage of the RNA phosphodiester backbone has been studied in aqueous solution and in a twister ribozyme from Oryza sativa. The free energy profiles associated with a baseline substrate-assisted mechanism for the reaction in the enzyme and in solution were computed by means of free energy perturbation methods within hybrid QM/MM potentials, describing the chemical system by the M06-2× functional and t…
A detailed identification study on high-temperature degradation products of oleic and linoleic acid methyl esters by GC–MS and GC–FTIR
2012
GC-MS and GC-FTIR were complementarily applied to identify oxidation compounds formed under frying conditions in methyl oleate and linoleate heated at 180ºC. The study was focused on the compounds that originated through hydroperoxide scission that remain attached to the glyceridic backbone in fats and oils and form part of non-volatile molecules. Twenty one short-chain esterified compounds, consisting of 8 aldehydes, 3 methyl ketones, 4 primary alcohols, 5 alkanes and 1 furan, were identified. In addition, twenty non-esterified volatile compounds, consisting of alcohols, aldehydes and acids, were also identified as major non-esterified components. Furanoid compounds of 18 carbon atoms form…
Nucleophilic substitutions on bromotriazolopyridines - an improved route to 2,6-disubstituted pyridines and to 1,3-disubstituted isoquinolines
1986
Abstract A regiospecific synthesis of 2,6-disubstituted pyridines and of 1,3-disubstituted isoquinolines is described.
Metallosupramolecular compounds based on Cu(ii)/oxalate/twisted NSSN ligands showing a new in situ S–C bond cleavage
2013
Four new complexes, [Cu2(C2O4) 2(SCS)]·3H2O (1), [Cu2(C 2O4)3(SCSH)2]·H2O (2), [Cu(C2O4)(SS)2]·3H2O (3) and [Cu(C2O4)(SS)]·6H2O (4) [where SCS = bis(4-pyridylthio)methane and SS = 4,4′-dipyridyldisulfide], have been synthesized by the reaction of the SS and SCS ligands with the corresponding copper(ii) oxalate salt. The different synthetic conditions allowed control of the preparation of a 3D open metal-organic framework in 1, a dinuclear zwitterionic molecular compound in 2 and one- and two-dimensional (1D and 2D) coordination polymers in 3 and 4, respectively. Compound 4 was also obtained by in situ transformation of the dithioether ligand (SCS) to the disulfide ligand (SS) under hydrothe…
Alkali-metal induced C,C-bond cleavage, C,H-bond cleavage, andcyclopolimerization in 1,5-hexadienes
1988
Abstract Reaction of the 1,5-dienes 3,4-homotropilidene ( 3 ) and 2,5-diphenylhexa-1,5-diene ( 4 ) with alkali metals induces C,H-bond cleavage (hydride formation) and cyclopolymerization, respectively, in contrast to the C,C-bond cleavage observed in semibullvalene and barbaralane.
Metal-free regioselective C–C bond cleavage in 1,3,5-triazine derivatives of β-diketones
2014
Metal-free regioselective activation of a carbon–carbon bond in 1,3,5-triazine derivatives of β-diketones is easily achieved, in the absence of a catalyst, with the assistance of intramolecular hydrogen bonding.