Search results for "Lewis"
showing 10 items of 271 documents
Interaction of half-sandwich alkylmolybdenum(III) complexes with B(C6F5)3. The X-ray structure of [CpMo(η4-C4H6)(μ-Cl)(μ-CH2)(O)MoCp][CH3B(C6F5)3]
2001
Abstract The reactions of the half-sandwich molybdenum(III) complexes CpMo(η 4 -C 4 H 4 R 2 )(CH 3 ) 2 , where Cpη 5 -C 5 H 5 and RH or CH 3 , with equimolar amounts of B(C 6 F 5 ) 3 have been investigated in toluene. EPR monitoring shows the formation of an addition product which does not readily react with Lewis bases such as ethylene, pyridine, or PMe 3 . The analysis of the EPR properties and the X-ray structure of a decomposition product obtained from dichloromethane, [CpMo(η 4 -C 4 H 6 )(μ-Cl)(μ-CH 2 )(O)MoCp][CH 3 B(C 6 F 5 ) 3 ], indicate that the borane attack has occurred at the methyl position.
A molecular electron density theory study of the insertion of CO into frustrated Lewis pair boron-amidines: a [4 + 1] cycloaddition reaction
2019
The insertion of CO into hydrogenated boron-amidine 1 yielding five-membered diazaborolone (5DAB) 3 has been studied within the molecular electron density theory (MEDT) at the DFT ωB97X-D/6-311G(d,p) level. This is a domino process comprised of two consecutive reactions: (i) the dehydrogenation of 1 yielding the frustrated Lewis pair (FLP) boron-amidine 4, which quickly equilibrates with four-membered diazaborolone (4DAB) 2; and (ii) the addition of CO into FLP 4, yielding the final 5DAB 3. Analysis of the Gibbs free energies indicates that the extrusion of H2 demands a high ΔG≠ of 28.6 kcal·mol-1, being endergonic by 6.7 kcal·mol-1. The subsequent addition of CO into FLP 4 presents a low Δ…
Field and petrographic evidence for partial melting of TTG gneisses from the central region of the mainland Lewisian complex, NW Scotland
2013
The central region of the mainland Lewisian complex is dominated by granulite-facies tonalite–trondhjemite–granodiorite (TTG) gneisses that are highly depleted in some mobile trace elements (Cs, Rb, Th and U) relative to amphibolite-facies TTG gneisses elsewhere in the Lewisian complex and to the average composition of TTG gneisses worldwide. Over almost half a century of research there has been vigorous debate as to the origin of this depletion, in particular with respect to the role of partial melting and melt loss. Here we provide field and petrographic evidence that TTG gneisses across the central region partially melted during granulite-facies (Badcallian) metamorphism. Partial melting…
Synthèse et caractérisation de phosphine, borane, amine sur plateforme ferrocène polyfonctionnelle
2016
Ferrocene platforms are useful in coordination chemistry and catalysis thanks to their robustness and versatile functionalization. Ferrocene backbone allows the implantation of several key functional groups in a restricted space, inducing close proximity and potential polyfunctional cooperation (see for instance ferrocenyl polyphosphine chemistry). Ansa ferrocene and ferrocene bearing conformational control inducing groups maximizing the proximity of key groups have been widely reported.The first part of this thesis focuses on the synthesis of new borylated cyclopentadienyl, and their use in formation of borylated metallocenes bearing conformational constraints. NMR analysis and DFT calcula…
On the enhancement of stereoselection by cooperation between chiral auxiliaries. Asymmetric diels-alder reactions with fumaric acid bis ((S)-proline …
1989
Abstract Fumaric acid bis ((S)-proline benzyl ester) amide reacts with cyclopentadiene in thermal and Lewis acid catalyzed Diels-Alder reactions to give the cycloadducts with high yields and diastereomeric ratios up to 100:1.
New constraints on granulite facies metamorphism and melt production in the Lewisian Complex, northwest Scotland
2018
The research carried out for this study was part of YF's Master Thesis at the Institute of Geoscience, Johannes Gutenberg University, Mainz, which provided the funding for fieldwork and laboratory analyses. TJ acknowledges support from Open Fund GPMR210704 from the State Key Lab for Geological Processes and Mineral Resources, China University of Geosciences, Wuhan. In this study we investigate the metamorphic history of the Assynt and Gruinard blocks of the Archaean Lewisian Complex, northwest Scotland, which are considered by some to represent discrete crustal terranes. For samples of mafic and intermediate rocks, phase diagrams were constructed in the Na2O-CaO‐K2O‐FeO‐MgO‐Al2O3-SiO2-H2O-T…
Heterometallic Titanium-Organic Frameworks as Dual Metal Catalysts for Synergistic Non-Buffered Hydrolysis of Nerve Agent Simulants
2020
Heterometallic metal-organic frameworks (MOFs) can offer important advantages over their homometallic counterparts to enable targeted modification of their adsorption, structural response, electronic structure, or chemical reactivity. However, controlling metal distribution in these solids still remains a challenge. The family of mesoporous titanium-organic frameworks, MUV-101(M), displays heterometallic TiM2 nodes assembled from direct reaction of Ti(IV) and M(II) salts. We use the degradation of nerve agent simulants to demonstrate that only TiFe2 nodes are capable of catalytic degradation in non-buffered conditions. By using an integrative experimental-computational approach, we rational…
Orientation of the acidity probes benzene, acetonitrile and pyridine in SAPO-5 and GaAPO-5 molecular sieves: an FTIR microscopy study
1997
The adsorption and desorption behaviour of benzene, acetonitrile (CD3CN) and pyridine for large crystals of SAPO-5 and GaAPO-5 is studied using FTIR microscopy with polarised IR radiation. From the analysis of the polarised adsorption bands it is concluded that the adsorbates are ordered in the molecular sieves at 373 K. The orientation of molecules interacting with Bronsted or Lewis acid sites and of physisorbed molecules are discussed. Benzene adsorbed at Bronsted sites is oriented with the aromatic ring parallel to the crystallographic c-axis of the molecular sieve, whereas physisorbed benzene is oriented with the aromatic ring parallel to the crystallographic a,bplane. Acetonitrile can …
Archaean Intracrustal Differentiation from Partial Melting of Metagabbro--Field and Geochemical Evidence from the Central Region of the Lewisian Comp…
2012
The central region of the mainland Lewisian gneiss complex of NW Scotland is a granulite-facies migmatite terrane. With the exception of ultramafic and rare calc-silicate rocks, all other lithologies partially melted during Neoarchaean, ultrahigh-temperature (Badcallian) metamorphism. The clearest evidence is preserved within large layered mafic^ultramafic bodies that exhibit macroscopic features diagnostic of anatexis. In situ partial melting of metagabbroic rocks produced patches and sheets of coarse-grained plagioclase-rich leucosome containing euhedral peritectic clinopyroxene.These leucosomes connect with larger, laterally continuous tonalite or trondhjemite sheets that record segregat…
Reversal of asymmetric induction in stereoselective strecker synthesis on galactosyl amine as the chiral matrix
1988
Abstract The reversal of the direction of asymmetric induction in Lewis acid catalyzed Strecker synthesis using the 2,3,4,6-tetra-O-pivaloyl-β-D-galactopyranosyl amine 1 is described. In isopropanol or tetrahydrofuran 1 had given ( R )-diastereomers of the corresponding α-amino nitriles preferably. However, in chloroform in the presence of heterogeneous zinc chloride the same auxiliary alternatively leads to an excess of the ( S )-diastereomers.