Search results for "bond"

The transport of ions across monoolein bilayers mediated by synthetic macrocyclic carriers

1989

The efficiency as carriers for the alkali and the alkaline earth ions across monoolein bilayers of three macrocyclic compounds has been investigated by conductometric measurements. The results show that although the three compounds have the optimum cavity size for fitting potassium and barium cations, their efficiency in ionic transport is quite different. These discrepancies are rationalized on the basis of the overlap of the water-diazacrown and cation-ligand interactions on the carrier mechanism.

Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C–H bond activation

2017

Abstract Synthesis, characterization and reaction chemistry of lutetium alkylamido LLu(CH2SiMe3)(NHCPh3) (2), L = 2,5-[Ph2P=N(4-iPrC6H4)]2N(C4H2)–, is reported. Complex 2 undergoes cyclometalation of the NHCPh3 ligand at elevated temperatures to produce the orthometalated complex LLu(κ2−N,C-(NHCPh2(C6H4))) (3) which converts to 0.5 equivalents of bis(amido) LLu(NHCPh3)2 (4) upon heating at 80 °C for 24 h. Reaction of complex 2 with 4-dimethylaminopyridine (DMAP) does not promote alkane elimination nor imido formation. A kinetic analysis of the thermal decomposition of complex 2, supported by deuterium labelling studies and computational analysis (PBE0/def2-TZVP/SDD(Lu)), indicate direct Csp…

Measuring the Relative Reactivity of the Carbon-Hydrogen Bonds of Alkanes as Nucleophiles

2018

We report quantitative measurements of the relative reactivities of a series of C-H bonds of gaseous or liquid CnH2n+2 alkanes (n = 1-8, 29 different C-H bonds) towards insitu generated electrophiles (copper, silver, and rhodium carbenes), with methane as the reference. This strategy surpasses the drawback of previous model reactions of alkanes with strong electrophiles suffering from C-C cleavage processes, which precluded direct comparison of the relative reactivities of alkane C-H bonds.

Nonporous Organic Solids Capable of Dynamically Resolving Mixtures of Diiodoperfluoroalkanes

2009

Halogen bonding has increasingly facilitated the assembly of diverse host-guest solids. Here, we show that a well-known class of organic salts, bis(trimethylammonium) alkane diiodides, can reversibly encapsulate α,ω-diiodoperfluoroalkanes (DIPFAs) through intermolecular interactions between the host's I – anions and the guest's terminal iodine substituents. The process is highly selective for the fluorocarbon that forms an I – ···I(CF 2 ) m I···I – superanion that is matched in length to the chosen dication. DIPFAs that are 2 to 12 carbons in length (common industrial intermediates) can thereby be isolated from mixtures by means of crystallization from solution upon addition of the dissolv…

Favoring alkane primary carbon-hydrogen bond functionalization in supercritical carbon dioxide as reaction medium

2019

The selectivity of a catalytic alkane functionalization process can be modified just changing the reaction medium from neat alkane to supercritical carbon dioxide (scCO2). A silica supported copper complex bearing an Nheterocyclic carbene ligand promotes the functionalization of carbon-hydrogen bonds of alkanes by transferring the CHCO2Et group from N2=CHCO2Et (ethyl diazoacetate, EDA). In neat hexane only 3% of the primary C-H bonds (ethyl heptanoate being the product) are functionalized in that manner, whereas the same reaction carried out in scCO2 provides a 30% yield in this linear ester. Such effect seems to be induced by an electronic density flux from the NHC ligand to the surroundin…

Pentacyanopropenide group as ligand in organometallic chemistry. Crystal structure and electrochemical studies of (Et4N)[W(CO)5{(C(CN)2C(CN)C(CN)2}]

1999

Abstract The title complex has been obtained by reaction of the tetraethylammonium pentacyanopropenide with tungsten hexacarbonyl in acetone. Its crystal structure involves discrete [W(CO)5{C3(CN)5}]− anions in which the organic fragment is N-coordinated via one of the nitrogen atoms of a cyano group borne by one of the terminal carbon atoms of the allylic skeleton. The anion presents a distorted octahedral coordination with a W–N bond length [2.168(5) A] considerably longer than the W–C bond lengths [cis-W–C in the range 1.998(7)–2.068(4) A; trans-W–C 1.962(7) A]. Cyclic voltammograms of this complex, recorded in CH2Cl2 and CH3CN (Bu4NPF6 0.1 M), display a quasi-reversible reduction and ir…

Haemostatic agents on the shear bond strength of self-adhesive resin

2015

Background Dentin surface contaminated with haemostatic agents can interfere with the bonding of self-adhesive resin cement. Therefore the purpose of this study was to evaluate the effect of various haemostatic agents such as Aluminium chloride, Ferric sulphate and Tannic acid on the shear bond strength of self-adhesive resin luting agent. Material and Methods The buccal surfaces of extracted premolars were flattened to expose the dentine. The teeth were then randomly divided into four groups. In Group I Aluminium Chloride was applied on the flattened dentinal surface, in Group II Ferric Sulphate was applied to exposed dentin surface, in Group III tannic acid was applied on to the dentinal …

Identification of a new series of amides as non-covalent proteasome inhibitors

2014

Proteasome inhibition has emerged as an important therapeutic strategy for the treatment of multiple myeloma (MM) and some forms of lymphoma, with potential application in other types of cancers. 20S proteasome consists of three different catalytic activities known as chymotrypsin-like (ChT-L), trypsin-like (T-L), and, post-glutamyl peptide hydrolyzing (PGPH) or caspase-like (C-L), which are located respectively on the β5, β2, and β1 subunits of each heptameric β rings. Currently a wide number of covalent proteasome inhibitors are reported in literature; however, the less widely investigated non-covalent inhibitors might be a promising alternative to employ in therapy, because of the lack o…

Unveiling the Chemo‐ and Regioselectivity of the [3+2] Cycloaddition Reaction between 4‐Chlorobenzonitrile Oxide and β‐Aminocinnamonitrile with a MED…

2021

Ab initio molecular orbital study of the substituent effect on ammonia and phosphine–borane complexes

2004

Abstract The complexation energies of H 3 BXH 3− n F n ( X =N, P; n =0–3) and the proton affinities of XH 3– n F n compounds have been investigated at the G2(MP2) level of theory. The G2(MP2) results show that the phosphine complexes are more stable than the corresponding ammonia ones. Increasing fluorine substitution on nitrogen atom reduces both the basicity of NH 3− n F n and the stability of ammonia complexes. For the phosphine complexes, the successive fluorine substitution on the phosphine increase the stability of H 3 BPH 3− n F n complexes although the reduction of the basicity of the PH 3– n F n ligands with this substitution. The NBO partitioning scheme shows that the stability of…