Search results for "BOND"
showing 10 items of 3527 documents
Computational Analysis of n→π* Back-Bonding in Metallylene–Isocyanide Complexes R2MCNR′ (M = Si, Ge, Sn; R = tBu, Ph; R′ = Me, tBu, Ph)
2013
A detailed computational investigation of orbital interactions in metal–carbon bonds of metallylene–isocyanide adducts of the type R2MCNR′ (M = Si, Ge, Sn; R, R′ = alkyl, aryl) was performed using density functional theory and different methods based on energy decomposition analysis. Similar analyses have not been carried out before for metal complexes of isocyanides, even though the related carbonyl complexes have been under intense investigations throughout the years. The results of our work reveal that the relative importance of π-type back-bonding interactions in these systems increases in the sequence Sn < Ge ≪ Si, and in contrast to some earlier assumptions, the π-component cannot be …
Plant-growth-regulating phosphono peptides
1990
Phosphono peptides exhibited plant‐growth‐regulating activity when tested on Lepidium sativum and Cucumis sativus. The studies have provided evidence that the mechanism of action of these compounds may involve the uptake of the phosphono peptides into the plant, intracellular hydrolysis of the peptide bond and release of the P‐terminal aminoalkylphosphonic acid. This acid or its metabolite is then probably responsible for the observed physiological effect.
Vergleichende dimerisierung der enantiomere von Oct-1-in-3-ol mit chiralen rhodium-phosphan-komplexen
1996
Abstract Three optically active phosphanes ([(S)-2-methylbutyl]3−nP[phenyl]n(n = 0, 1, 2), were tested as ligands in rhodium(I) complexes to form catalysts for the enantioselective dimerisation of (R)- and (S)-oct-1-yn-3-ol. The catalytic reaction provides enantioselectivity for this type of CC bond formation. For reactions at 45–75°C and depending on the P-ligand used the rates vary for both enantiomers from 6:1 to 50:1 in favour of the (S)-octynol.
Reaktionen von Benzothiet mit Iminen
1993
Reactions of Benzothiete with Imines A great variety of compounds 3a–w containing CN double bonds was studied in the reaction with benzothiete (1). H, alkyl, aryl, OR, SR and NR groups can be attached to the imino function. The azomethines 3a–f, the thiazolines 3g–i, the lactim 3n, the oximes 3r–t, the isoxazolinone 3u and the azine 3v show [8π + 2π] cycloaddition reactions yielding derivatives of 1,3-benzothiazine (4a–i, n, r–v). In the case of 4n, s, t secondary reactions occur, initiated by elimination processes. [8π + 2π] Cycloadditions account also for the reactions 3e 10, 11, 3o 18(I), and 3q 19; however, CC double bonds are representing the 2π component in these examples. The thiazol…
Thermal Rearrangements of Perchlorohexatrienes-Structures and Experimental and Theoretical Evaluation of Pathways to Isomerization and Cyclization
2009
We have prepared trans- (1) and cis-octachloro-1,3,5-hexatriene (2) by known routes and studied their thermal behavior experimentally and theoretically by ab initio calculations. The three double bonds in 1 and 2 are completely decoupled due to steric hindrance by the eight Cls, as indicated by calculations as well as the single-crystal X-ray structure of 1. The cis isomer 2 can be isomerized to the trans isomer 1 by heating it to 220–250 °C either neat or dissolved in high-boiling solvents, leading to a roughly 2:1 mixture of trans and cis isomers. Calculations at several different levels of theory predict 1 and 2 to be isoenergetic within 2 kJ mol–1. Unimolecular cis/trans isomerization i…
Thermodynamics of binary mixtures: Volumes, heat capacities, and dilution enthalpies for then-pentanol+2-methyl-2-butanol system
1983
The densities, heat capacities, and dilution enthalpies ofn-pentanol+2-methyl-2-butanol mixtures have been measured, in many cases as a function of temperature, over the complete mole fraction range. Excesses thermodynamic properties, apparent and partial molar heat capacities, volumes and expansibilities were derived. The concentration and temperature dependences of these functions are discussed in terms of the variations of the structure of the system caused by the participation of the two alcohol molecules (with quite different steric hindrance of the alkyl chain around the-OH group) in the dynamic intermolecular association process through hydrogen bonding.
Cooperative Binding of Divalent Diamides by N-Alkyl Ammonium Resorcinarene Chlorides
2015
N-Alkyl ammonium resorcinarene chlorides, stabilized by an intricate array of hydrogen bonds leading to a cavitand-like structure, bind amides. The molecular recognition occurs through intermolecular hydrogen bonds between the carbonyl oxygen and the amide hydrogen of the guests and the cation-anion circular hydrogen-bonded seam of the hosts, as well as through CH⋅⋅⋅π interactions. The N-alkyl ammonium resorcinarene chlorides cooperatively bind a series of di-acetamides of varying spacer lengths ranging from three to seven carbons. Titration data fit either a 1:1 or 2:1 binding isotherm depending on the spacer lengths. Considering all the guests possess similar binding motifs, the first bin…
Molecular self-assembly on an insulating surface: interplay between substrate templating and intermolecular interactions
2012
We report on molecular self-assembly of biphenyl-4,4'-dicarboxylic acid (BPDCA) on CaCO3(10 (1) over bar4) under ultra-high vacuum conditions. Two-dimensional, ordered islands are obtained upon deposition at room temperature, coexisting with a streaky structure that is ascribed to individual, mobile molecules forming a two-dimensional gas-like phase. High-resolution non-contact atomic force microscopy (NC-AFM) images of the molecular islands reveal an ordered inner structure that is dominated by rows of molecules aligned side by side running along the [(42) over bar 61] crystallographic direction. A detailed analysis of these rows exhibits inter-row distances that are multiples of the calci…
A green route to synthesize poly(lactic acid)-based macromonomers in scCO2 for biodegradable nanoparticle production
2014
Poly(lactic acid)-based macromonomers, aimed at biomedical applications and with well-defined average chain length, are produced through catalytic ring-opening polymerization of L,L-lactide co-initiated by a co-monomer bearing a double bond. Reactions have been carried out in supercritical carbon dioxide (scCO2) at different temperatures, ranging from 90 to 130 °C. The resulting oligomers have been characterized by different techniques (1H-NMR, 13CNMR, MALDI-TOF, ESI, GPC, FT-IR, TGA), which show that oligomers with narrower molecular weight distribution are produced at the lowest temperature. In addition, a significant reduction of the impact of the secondary reactions has been found at th…
Hetero-Multifunctional Poly(ethylene glycol) Copolymers with Multiple Hydroxyl Groups and a Single Terminal Functionality
2009
Hetero-multifunctional poly(ethylene glycol-co-glycerol) random copolymers with multiple hydroxyl functionalities and a single terminal functionality have been prepared by copolymerization of ethylene oxide (EO) and ethoxy ethyl glycidyl ether (EEGE) with the use of a suitable initiator, introducing a protected amino group or a double bond, respectively. Acidic deprotection was used for removal of the acetal protecting groups in the chain, and the terminal amino group was regenerated by catalytic hydrogenation. A series of copolymers with narrow polydispersity was obtained, varying comonomer fractions from 3 to 67% and molecular weights in the range of 5 000-32 000 g · mol(-1) (1.05 < $\ove…