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The enhanced optical stability of sterically hindered triorganotin halides

Published on Sep 1, 2010in Bulletin des Sociétés Chimiques Belges
· DOI :10.1002/bscb.19750841103
Marcel Gielen35
Estimated H-index: 35
(Vrije Universiteit Brussel),
Hassan Mokhtar-Jamaï4
Estimated H-index: 4
(ULB: Université libre de Bruxelles)
Abstract
The optical stability of methylneophyltrityltin halides is greater than that of less sterically hindered triorganotin halides.
  • References (19)
  • Citations (11)
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References19
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#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 25
#2Hassan Mokhtar-Jamaï (ULB: Université libre de Bruxelles)H-Index: 4
The synthesis of optically active p‐anisyl‐(3‐hydroxy‐3‐methylbutyl)methyl‐α‐naphthyl tin (IV) is described. The spectroscopic properties of this compound and of the products used as synthesis intermediates are given. The two diastereoisomers of (‐)‐menthyl‐β‐(methylnaphthyl‐phenylstannyl)‐propionate (V) could not be separated. Copyright © 1975 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
25 CitationsSource
#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 25
#2Stéphane Simon (Vrije Universiteit Brussel)H-Index: 1
Last. Cornelis Hoogzand (Vrije Universiteit Brussel)H-Index: 9
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Methylneophylphenyltin hydride (I), (methylneophylphenylstannyl) cyclopentadienyl molybdenum tricarbonyl(II) and dimethylphenylstannylmethyl-α-naphthyl-phenylgermanium (III) are configurationally stable within the NMR time scale, even in the presence of strong nucleophiles.
12 CitationsSource
#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 35
#2Hassan Mokhtar-Jamaï (ULB: Université libre de Bruxelles)H-Index: 4
Abstract Determination of the concentrations of pyridine required to cause coalescence of the neophylic methyl group resonances at 60, 100 and 270 MHz has shown that the racemisation of methylneophyl-t-butyltin chloride or bromide in benzene is of second order in the nucleophile.
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#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 35
#2Hassan M. Jamaï (ULB: Université libre de Bruxelles)H-Index: 1
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#1Kensuke Takahashi (Nagoya Institute of Technology)H-Index: 11
#2Takeshi Akasaka (Nagoya Institute of Technology)H-Index: 1
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The 60 MHz 1H NMR spectra of p-substituted phenyl 2-chloro-2-fluoroethyl sulphides have shown characteristic patterns; in the ABC portion of an ABCX spin system (X = 19F) of the compounds, one of the subspectra shows an ABC pattern and the other apparently an AB2 pattern. These spectral patterns have been analysed and the 1H NMR data obtained are discussed briefly.
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An extensive series of complexes [(cp)Col(L)RF][L = phosphorus donor; RF= CF3, CF2CF3, or CF(CF3)2] and [(cp)CoCO(PPh3)CF2CF3]ClO4(cp =π-cyclopentadienyl), many of them hitherto unreported, have been prepared and characterized. Variable-temperature proton and fluorine n.m.r. spectra of several of the complexes provide evidence for hindered rotation about both metal–carbon and phosphorus–aryl bonds, while the i.r. spectrum of the carbonyl complex suggests the presence of diastereoisomers, the co-...
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Summary 10,10-Dimethyl- and 10,10-diethylphenoxastannin have been prepared for the first time by the reaction of oxy-2,2′-bis (phenyllithium) with dimethyl- and diethyltin dichloride, respectively. The compound thought by Kupchik et al. to be dimeric 10,10-dimethylphenoxastannin has been found to be a twelve-membered organotin heterocycle, C 28 H 28 O 2 Sn 2 . PMR spectra in various solvents show this compound to be present in solution as an equilibrium mixture of conformational isomers. The PMR...
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Chemical shift non-equivalence of diastereotopic groups has been studied for a series of organotin monohalides with organic groups of different sizes to test the stereochemical stability of the asymmetric tin centre. The mutually related effects of halogen intermolecular exchange, nature of tin–halogen bond, intrinsic asymmetry of the molecules, and the steric requirements of the organotin groups are discussed in the light of the experimental findings. The effect of the bulk of the organic group...
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Cited By11
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#1Jean-Paul Quintard (University of Nantes)H-Index: 22
#2E. Le Grognec (University of Nantes)H-Index: 19
The synthesis of chiral molecules or complexes containing tin(IV) and tin(II) is reported considering the type of chirality and the nature of the bonding to tin. The tin-centered chirality is first examined considering different types of functionalization and focusing on the configurational stability at the tin center, which provides useful information for organometallic chemists. Chiral ligands C -linked, O -linked, or N -linked to tin have been subsequently considered focusing first on the syn...
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#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 25
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#1M. Belén Faraoni (UNS: Universidad Nacional del Sur)H-Index: 3
#2A. D. Ayala (UNS: Universidad Nacional del Sur)H-Index: 7
Last. Julio C. Podestá (UNS: Universidad Nacional del Sur)H-Index: 13
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A key step in the preparation of asymmetric heterogeneous catalysts based on silica-supported rhodium and platinum chemically modified with chiral organotins, is the synthesis of optically pure tin derivatives. We report on the synthetic pathways leading to the synthesis of (−)-menthyltin derivatives without the formation of epimerization by-products. The physical properties (including full 1H, 13C and 119Sn NMR spectra) of the new compounds, containing between one and three (−)-menthyl ligands ...
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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 35
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An overview is given of the research performed by the authors at the Universite Libre de Bruxelles and Vrije Universiteit Brussel, including the kinetics, stereochemistry and mechanism of SE2 reactions at a saturated carbon atom, the synthesis of chiral organotin compounds and their configurational and optical stability, the fluxionality of trigonal bipyramidal metal atoms and the stereochemistry of SN2 reactions at tetrahedrally substituted P, Si, Ge, Sn atoms, the cytotoxicity of many series o...
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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 35
#2Klaus Jurkschat (Vrije Universiteit Brussel)H-Index: 34
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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 35
Many organotin compounds are optically stable for long periods so that all the reactions transforming one of them into another can be studied from the stereochemical point of view. Several stereoselective reactions at tin have already been found. However the stereochemistries and even the stereoselectivities have not yet been determined (if the H—D exchange is not taken into account) because the optical purities (and a fortiori the absolute configurations) of the starting materials and of the re...
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#1Hans-Ulrich Buschhaus (Technical University of Dortmund)H-Index: 1
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Thermische und reversible Dissoziation organischer Distannane R3Sn-SnR3 (1) ⇄ 2 R3Sn. (2) konnte erstmalig nachgewiesen werden, wenn durch sperrige Reste R eine genugende Spannung in 1 erzeugt wurde. Bis 230°C reichen die Reste R = Phenyl, Cyclohexyl, 1-Adamantyl hierfur nicht aus, jedoch mit R = 2,4,6-Trialkylphenyl sinkt die Dissoziationstemperatur (ESR) in der Reihe Alkyl = Me, Et, iPr bis auf 20°C ab. ESR-Spektren der Stannylradikale 2 sowie vSn-Sn(sym.)-[Raman], δHDiss.- und EA-Werte fur 1 ...
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Die Oxidation und Halogenierung von (o-Triorganostannylbenzyl)-diorganophosphinen, dargestellt aus o-Lithiobenzyl-diorganophosphinen und Triorganozinnhalogeniden, liefert die [(o-Diorganophosphinylmethyl)-phenyl]-diorganozinnhalogenide 6–10. IR-, 1H-und 31P-NMR-Daten bestatigen fur 6–10 eine komplexcyclische struktur mit pentakoordiniertem Zinn. Aus der Temperaturabhangigkeit der 1H-NMR-Spektren folgt ein Konfigurationswechsel am Zinn. Atom in diesen Verbindungen. Synthesis, Structure, and Molec...
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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 25
#2Ivan Vanden Eynde (Vrije Universiteit Brussel)H-Index: 6
The configurational stability of triorganostannyl–iron, –manganese and –cobalt complexes has been determined by studying the coalescence of the NMR signals of diastereotopic groups and by looking at the epimerization of diastereomeric mixtures of these compounds. Possible substitution reactions, transforming the studied derivatives into one another, have been checked.
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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 25
#2Yves Tondeur (ULB: Université libre de Bruxelles)H-Index: 6
Optically active triorganotin hydrides have been synthesized by asymmetric reduction of the corresponding halides. These optically stable compounds undergo stereoselective conversions into other optically stable compounds such as tetraorganotin compounds (by reaction with diazomethane or with bifluorenylidene) or hexaorganoditin compounds (by reaction in the presence of palladium) or into optically unstable compounds such as methylneophylphenyltin chloride (by reaction with CCl4). The HD exchan...
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