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FLP reactivity of [PhC] and (o-tolyl)P and the capture of a Staudinger reaction intermediate.
Dalton Trans
July 2017
Department of Chemistry, University of Toronto, 80 St George St., Toronto, Ontario M5S 3H6, Canada.
The frustrated Lewis pair (FLP) derived from the trityl cation and (o-tolyl)P effects the activation of 1,4-cyclohexadiene and 1-bromo-4-ethynylbenzene and heterolytically cleaves the S-S bond of diphenyl disulfide. The FLP also captures pentafluorophenyl azide as the Staudinger reaction intermediate, a species that reacts with PhSiH to give the silyl analog.
View Article and Find Full Text PDFCationic Five-Coordinate Bis(guanidinato)silicon(IV) Complexes with SiN4 El Skeletons (El=S, Se): "Heterolytic Activation" of S-S and Se-Se Bonds.
Chemistry
April 2016
Universität Würzburg, Institut für Anorganische Chemie, Am Hubland, 97074, Würzburg, Germany.
The donor-stabilized silylene [iPrNC(NiPr2 )NiPr]2 Si (2) reacts with PhEl-ElPh (El=S, Se) to form the respective cationic five-coordinate bis(guanidinato)silicon(IV) complexes {[iPrNC(NiPr2 )NiPr]2 SiSPh}(+) PhS(-) (4) and {[iPrNC (NiPr2 )NiPr]2 SiSePh}(+) PhSe(-) (5). Compounds 4 and 5 were characterized by crystal structure analyses and NMR spectroscopic studies in the solid state.
View Article and Find Full Text PDFExploiting metal-ligand bifunctional reactions in the design of iron asymmetric hydrogenation catalysts.
Acc Chem Res
May 2015
Department of Chemistry, University of Toronto, 80 Saint George Street, Toronto, Ontario M5S3H6, Canada.
This is an Account of our development of iron-based catalysts for the asymmetric transfer hydrogenation (ATH) and asymmetric pressure hydrogenation (AH) of ketones and imines. These chemical processes provide enantiopure alcohols and amines for use in the pharmaceutical, agrochemical, fragrance, and other fine chemical industries. Fundamental principles of bifunctional reactivity obtained by studies of ruthenium catalysts by Noyori's group and our own with tetradentate ligands with tertiary phosphine and secondary amine donor groups were applied to improve the performance of these first iron(II) catalysts.
View Article and Find Full Text PDFUnravelling the mechanism of the asymmetric hydrogenation of acetophenone by [RuX2(diphosphine)(1,2-diamine)] catalysts.
J Am Chem Soc
March 2014
Chemistry Division, MS J582, and ‡Theoretical Division, MS B268, Los Alamos National Laboratory , Los Alamos, New Mexico 87545, United States.
The mechanism of catalytic hydrogenation of acetophenone by the chiral complex trans-[RuCl2{(S)-binap}{(S,S)-dpen}] and KO-t-C4H9 in propan-2-ol is revised on the basis of DFT computations carried out in dielectric continuum and the most recent experimental observations. The results of these collective studies suggest that neither a six-membered pericyclic transition state nor any multibond concerted transition states are involved. Instead, a hydride moiety is transferred in an outer-sphere manner to afford an ion-pair, and the corresponding transition state is both enantio- and rate-determining.
View Article and Find Full Text PDFtrans-Fe(II)(H)2(diphosphine)(diamine) complexes as alternative catalysts for the asymmetric hydrogenation of ketones? A DFT study.
Dalton Trans
January 2011
Kathleen Lonsdale Building, Department of Chemistry, University College London, Gower Street, London, United Kingdom WC1E 6BT.
New insights into the structural, electronic and catalytic properties of Fe complexes are provided by a density functional theory study of model as well as real [Fe(II)(H)(2)(diphosphine)(diamine)] systems. Calculations conducted using several different functionals on the trans- and cis-isomers of [Fe(II)(H)(2)(S-xylbinap)(S,S-dpen)] complexes show that, as with the [Ru(II)(H)(2)(diphosphine)(diamine)] complexes, the trans-[Fe(II)(H)(2)(diphosphine)(diamine)] complex is the more stable isomer. Analysis of the spin states of the trans-[Fe(II)(H)(2)(diphosphine)(diamine)] complexes also shows that the singlet state is significantly more stable than the triplet and the quintet, as with the [Ru(II)(H)(2)(diphosphine)(diamine)] complexes.
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