Search results for "steric"
showing 10 items of 476 documents
Sterically controlled self-assembly of tetrahedral M(6)L(4) cages via cationic N-donor ligands.
2014
Tripodal cationic N-donor ligands exhibit sterically controlled self-assembly of tetrahedral M6L4 coordination cages that promote selective anion encapsulation (PF6(-)OTf(-)) in the solid state. The described method is a potential template for stepwise assembly of hetero-ligand coordination cages and polymers.
Structure and Conformational Studies of Aza-Crown 8-Amino-BODIPY Derivatives: Influence of Steric Hindrance on Their Photophysical Properties
2017
Herein, we report the synthesis, X-ray crystal structure and photophysical studies of six new 8-amino-BODIPY derivatives containing crown or azo-crown ether moieties. The influence of steric hindrance, caused by the crown ether, on the planarity of the BODIPY core and its relationship with the fluorescent properties has been established. 1H NMR spectroscopic studies were undertaken to clarify the changes in fluorescence observed in the presence of ZnII.
Synthesis and Reactivity of New Chelate-N-Heterocyclic Biscarbene Complexes of Ruthenium
2004
The carbene-ligand precursors methylenebis(N-alkylimidazolium) iodide (alkyl = methyl, neo-pentyl) and ethylenebis(N-methylimidazolium) chloride have been used in the preparation of several new Ru(II)-p-cymene complexes where the ligand behaves as mono- and bidentate. The molecular structures of the two biscarbene-complexes are reported. From the data reported, we can conclude that steric reasons (mainly the bisimidazolium linkers, methylene/ethylene) are the main factors determining both reactivity and synthetic difficulties of the products reported.
Vergleichende Untersuchung zur Diastereoselektivität derO-Methylierung von sterisch behinderten β-Ketocarbonsäureestern und ihren Enolen
1990
Diastereoselectivity of the O-Methylation of Sterically Hindered β-Ketocarboxylates and Their Enols The enols 1a, b, and 1c, which exists almost completely in the keto form, have been methylated at the oxygen atom with diazomethane. The regioselective reaction can be catalyzed by methanol, but may loose in that case the diastereoselectivity. A comparison with the methylation of the enolates by iodomethane is discussed.
ChemInform Abstract: In situ DRIFT Spectroscopic Investigation on the Chemical Evolution of Zinc Phosphate Acid-Base Cement.
2010
Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy has been used to follow the chemical evolution of zinc phosphate acid−base cement (ZPC), which has been prepared from unmodified, as well as from aluminum- and zinc-modified orthophosphoric acid. For the first time, amorphous dizinc cyclotetraphosphate octahydrate, Zn2P4O12·8H2O, although hydrolytically instable, has been observed as precursor phase prior to crystallization of α-hopeite, α-Zn3(PO4)2·4H2O, in both systems. Within minutes from onset of mixing the infrared spectrum of unmodified ZPC is dominated by the characteristic vibrations of α-hopeite, due to matrix crystallization. Setting of modified ZPC is strongly af…
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…
Glycosidsynthese mit 2,3,4,6-Tetra-O-pivaloyl-α-D-glucopyrancsylbromid
1982
Die Glycosylierung von Benzylalkohol und Cholesterin gelingt mit 2,3,4,6-Tetra-O-pivaloyl-α-D-glucopyranosylbromid (2) in Gegenwart von Silbersalzen in hoher Ausbeute. Die bei Koenigs-Knorr-Synthesen mit 2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosylbromid (5) storende Orthoesterbildung wird beim Einsatz von 2 weitgehend unterdruckt. Die Lenkung der Reaktion zugunsten der Glycosidbildung wird dadurch erklart, das der tert-Butyl-Substituent im zwischenzeitlich gebildeten Acyloxoniumion A den nucleophilen Angriff am Acyloxoniumkohlenstoff sterisch behindert. Glycoside Synthesis Using 2,3,4,6-Tetra-O-pivaloyl-α-D-glucopyranosyl Bromide In the presence of silver salts the glycosylation of benzyl alc…
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.
The oligomerisation of phenylacetylenes with rhodium(I) and P ligands as the catalytic system
1991
Abstract The dependence of the oligomerisation of phenylacetylene to cyclotrimers and dimers upon a Rh(I) complex with different P ligands as the catalytic system has been studied. The influence of substituents in the phenyl ring of the substrate has been examined as well. A selective cyclotrimerisation of phenylacetylenes is achieved with [1,5-C6H10RhCl]2 as the catalyst. A decrease of the selectivity appears with very bulky o-substituents or a substitution in the 2,6-position of phenylacetylene. [P]-control maps indicate a mono-association of the ligand accompanied by a reduced activity of the system. The second association of a P ligand results in an inhibition of the cyclotrimerisation …
Rare earth metal complexes that contain linked amido-cyclopentadienyl ligands: ansa-metallocene mimics and “constrained geometry” catalysts
2003
A survey of group 3 metal complexes that contain a linked amido-cyclopentadienyl ligand is given. Originally designed as ansa-metallocene analogues for the development of single-component olefin polymerization catalysts, variations in the metals and ligand substituents have allowed the synthetic access to new rare earth metal complexes including olefin polymerization initiators, divalent complexes and heterobimetallic metallocenes. The linked amido-cyclopentadienyl ligands have made half-sandwich complexes of group 3 metals accessible in a more systematic manner and provided a better understanding of the electronic and steric constraints of chelating ligands for the larger rare earth metal …