Structures formed by the chiral assembly of racemic mixtures of enantiomers: iodination products of elaidic and oleic acids

The self-assembled monolayer structure of the products of elaidic acid iodination (the racemic mixture of 9,10-(9S,10R)-diiodooctadecanoic acid and 9,10-(9R,10S)-diiodooctadecanoic acid) and the products of oleic acid iodination (the racemic mixture of 9,10-(9R,10R)-diiodooctadecanoic acid and 9,10-(9S,10S)-diiodooctadecanoic acid) are studied by high-resolution scanning tunneling microscopy. For the iodination products of elaidic acid, the separation of enantiomers into distinct chiral domains during the formation of the 2-D crystal on the highly ordered pyrolytic graphite (HOPG) surface is not observed. Instead, within the diiodooctadecanoic acid SAM, each row of molecules is composed of opposite racemates. The two opposite racemates pack alternately inside a row, using different faces to adsorb on the surface. The unit cell is composed of a pair of opposite racemates, forming a heterochiral structure. For the iodination products of oleic acid, the racemic mixture is observed to exhibit quasi-phase separation during the formation of the 2-D crystal on the HOPG surface. Each row is composed of homochiral acid molecules, either the 9,10-(9R,10R)-diiodooctadecanoic acid (R) or the 9,10-(9S,10S)-diiodooctadecanoic acid (S). The R row and the S row pack alternately, with a unit cell composed of four molecules. Two of the molecules in the unit cell are the 9,10-(9R,10R)-diiodooctadecanoic acid (R) molecules; two are the 9,10-(9S,10S)-diiodooctadecanoic acid (S) molecules. In the unit cell, the two molecules that have the same chirality pack antiparallel inside the homochiral row, using different faces to adsorb on the surface. These results suggest that several different types of chiral assembly are possible. Enantiomers with opposite chirality exhibit many chiral assembly patterns, forming heterochiral structures on the surface in addition to separation to form macroscopic chiral domains. By using different conformations, similar enantiomers with opposite chirality will display many chiral assembly patterns to form heterochiral structures on the surface.     

Direct observation of eta 2-imine formation through beta-H abstraction between amide ligands. Neutron and X-ray diffraction structure of a dihydride imine ditantalum complex

Reactions of Ta(NMe2)5 with D2SiR'Ph (R' = Me, Ph) were found to give a dideuteride eta 2-imine complex (Me2N)3Ta(mu-D)2(mu-N-eta 2-N,C-CH2NMe)Ta(NMe2)3(1-d2) through C-H activation of an amide ligand via beta-H abstraction, and the structure of 1 was confirmed by single crystal neutron and X-ray diffraction.     

A new synthesis of 2-fluoro-1-naphthols

A general synthesis of 2-fluoro-1-naphthols in two steps from 1-indanones is reported. The 1-indanones are first converted to difluoromethyl 2-fluoro-1-napthyl ethers by reaction with difluorocarbene source, trimethylsilyl 2-fluorosulfonyl-2,2-difluoroacetate (TFDA). These ethers are then converted in high yield to the respective naphthols by heating with a mixture of acetic acid and 48% HBr.     

The uranium-Xylidyl Blue I complex and its application in linear sweep polarography

The linear sweep polarographic wave of the uranium-Xylidyl Blue I complex in ethylenediamine-1,10-phenanthroline-hydrochloric acid medium has been studied. The complex, corresponding to UO(2)(XBI)(2-)(2) with log beta' = 9.09 (by polarography), 8.81 (by spectrophotometry), is strongly adsorbed on the surface of the mercury electrode. The polarographic wave is attributed to the reduction of Xylidyl Blue I in the complex. The method is very sensitive with a detection limit of 3 x 10(-8)M. The wave height is proportional to the concentration of uranium over the range 8 x 10(-8)-7 x 10(-6)M. Solvent extraction is used to separate possible interferences. The recommended procedure has been applied to the determination of trace amounts of uranium in ores.     

Carbonyl allylation of aldehydes catalyzed by a silica-supported poly-γ-diphenylarsinopropylsiloxane palladium(0) complex

A silica-supported poly-γ-diphenylarsinopropylsiloxane palladium(0) complex has been prepared from γ-chloropropyltriethoxysilane via immobilization on fumed silica, followed by reacting with potassium diphenylarsenide and palladium chloride, and then the reduction with hydrazine hydrate. The palladium(0) complex has been found to catalyze the allylation of aldehydes via the formation of π-allylpalladium complexes, using allylic chlorides as allylating agent and SnCl₂ as reducing agent. This polymeric palladium complex can be recovered and reused.     

Reactivity of organolanthanide and organolithium complexes containing the guanidinate ligands toward isocyanate or carbodiimide: synthesis and crystal structures

The direct reactions of (C5H5)2LnCl with LiN=C(NMe2)2 proceeded at room temperature in THF under pure nitrogen to yield the lanthanocene guanidinate complexes [(C5H5)2Ln(mu-eta1:eta2-N=C(NMe2)2)]2 (Ln = Gd (1), Er (2)). Treatment of phenyl isocyanate with complexes 1 and 2 results in monoinsertion of phenyl isocyanate into the Ln-N(mu-Gua) bond to yield the corresponding insertion products [(C5H5)2Ln(mu-eta1:eta2-OC(N=C(NMe2)2)NPh)]2 (Ln = Gd (3), Er (4)), presenting the first example of unsaturated organic small molecule insertion into the metal-guanidinate ligand bond. Further investigations indicate that N,N'-diisopropylcarbodiimide does not react with complexes 1 and 2 under the same conditions; however, it readily inserts into the lithium-guanidinate ligand bond of LiN=C(NMe2)2. As a synthon of the insertion product Li[(iPrN)2C(N=C(NMe2)2)], its reaction with (C5H5)2LnCl gives the novel organolanthanide complexes containing the guanidinoacetamidinate ligand, (C5H5)2Ln[(iPrN)2C(N=C(NMe2)2)] (Ln = Yb (5), Er (6), Dy (7)). All complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 1, 3, 5 and 7 were determined through X-ray single-crystal diffraction analysis.     

Synthesis of new 1,3-bis（phenylethynyl）disilazanes

Three new 1,3-bis(phenylethynyl)disilazanes were synthesized from the reaction of 1,3-dichlorodisilazanes with (phenylethy- nyl)lithium,and characterized by infrared (IR) spectra,nuclear magnetic resonance (NMR) and mass spectrometry (MS).     

Theoretical formalism and experimental verification of line shapes of NMR intermolecular multiple-quantum coherence spectra

Although the theories and potential applications of intermolecular multiple-quantum coherences (iMQCs) have been under active investigations for over a decade, discussion of iMQC NMR signal formation was mainly confined in the time domain. In this paper, a full line-shape theory was developed to describe iMQC signals in the frequency domain. Relevant features of the line shape, such as peak height, linewidth, and phase, were investigated in detail. Predictions based on the theory agree well with experimental and simulated results. Since radiation-damping effects always couple with iMQCs in highly polarized liquid-state NMR systems, and strongly radiation-damped signals have many spectral characteristics similar to those of iMQCs, a detailed comparison was also made between them from different spectral aspects. With detailed comparison of peak height, linewidth, and phase, this work demonstrates that the iMQC and radiation-damping phenomena result from two completely different physical mechanisms despite that both present similar signal features and coexist in highly polarized liquid-state NMR systems.