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Diastereotopic nonequivalence in organotin compounds: Preliminary communication

Published on Sep 2, 2010in Recueil des Travaux Chimiques des Pays-Bas
· DOI :10.1002/recl.19690881111
Marcel Gielen4
Estimated H-index: 4
(ULB: Université libre de Bruxelles),
M. De Clercq4
Estimated H-index: 4
(ULB: Université libre de Bruxelles)
+ 3 AuthorsH. Vanwuytswinkel1
Estimated H-index: 1
(ULB: Université libre de Bruxelles)
Abstract
  • References (9)
  • Citations (9)
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References9
Newest
A redistribution of s-character in the tin orbitals of the Sn–C bonds of methyl-substituted tetraorganotins R3SnR' are expected to depend on the steric requirements of the R and R' groups and might be held responsible for the differences found for the J(Sn–C–H) coupling constants.
5 CitationsSource
#1Stéphane Boué (ULB: Université libre de Bruxelles)H-Index: 8
#2Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 38
Last. Jacques Nasielski (ULB: Université libre de Bruxelles)H-Index: 10
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The mass spectra of mixed tetraalkyltins are described and analysed. The fragmentation pattern is in agreement with the hypothesis of prefered Sn(IV) and Sn(II) valence states in the tin‐containing fragments. These states are reached by losing an alkyl radical from the next higher unfavourable valence state, or by losing an alkene or alkane molecule from a favourable valence state. The ease of cleavage of a carbon‐tin bond in the molecular ion parallels the stabilization of the leaving alkyl rad...
32 CitationsSource
#1Stéphane Boué (ULB: Université libre de Bruxelles)H-Index: 8
#2Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
Last. Richard Spielmann (ULB: Université libre de Bruxelles)H-Index: 2
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Nine new racemic organotin derivatives: MePriPrSnR (R = Br, Et, Bu, iBu, sBu, tBu) and MeiPrcycloHexSnR′ (R′ = Br, Et, anisyl) have been synthesized in high yields. Their mass spectra and those of some intermediates are given and discussed on the basis of previous results. Copyright © 1969 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
23 CitationsSource
#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
#2Jacques Nasielski (ULB: Université libre de Bruxelles)H-Index: 13
Last. J. Topart (ULB: Université libre de Bruxelles)H-Index: 7
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18 CitationsSource
#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 38
#2Jacques Nasielski (ULB: Université libre de Bruxelles)H-Index: 10
The mass spectra of a series of aryltrimethyltins are described and analysed. The main features are: a relatively weak molecular ion, a very important ArSnMe2+ ion (base peak), a low intensity ArSnMe+ fragment and a non negligible ArSn+ peak. These findings may be related to the well known stable valence states of tin (IVSn and IISn) and the unfavourable IIISn and ISn states. Whereas a methyl group is easier to cleave from the ArSnMe3+ ion than the phenyl radical, n-butyl seems to be more strong...
20 CitationsSource
#1Marcel Gielen (Free University of Brussels)H-Index: 38
#2M. De Clercq (Free University of Brussels)H-Index: 3
Last. Jacques Nasielski (Free University of Brussels)H-Index: 10
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Matrix representations are given for five-coordinate structures (product matrices P) and for the intramolecular isomerization reactions of these complexes (reaction matrices R) via pseudo-rotation processes. Matrix transformations are also described, which allow to deduce from the general case the subset of rearrangements generated by various constraints (using constraint matrices C). Several examples are depicted and compared with previous descriptions.
17 CitationsSource
#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
#2G. Mayence (ULB: Université libre de Bruxelles)H-Index: 5
The mass spectra of four different series of trialkyltin halides are described and analysed. The fragmentation rules are found to be identical to those of other alkyltin systems. The fragmentation pattern conforms to hypothesis of preferred SnIV and Sn11 valence state in the tin-containing fragments. The ease of cleavage of a halogen-tin bond in the molecular ion parallels the bond energy in the ground state.
40 CitationsSource
#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
#2Jacques Nasielski (ULB: Université libre de Bruxelles)H-Index: 13
Abstract The very similar sensitivity of the iododemetallation of tetraalkyltins and -leads to solvent effects suggests close similarity between the mechanisms of cleavage of CSn and CPb bonds; bond-breaking seems to be the rate-determining factor. The importance of nucleophilic assistance in this type of reactions is emphasized.
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Resume La vitesse de la reaction des tetraalkyletains avec les halogenes a ete determinee dans une serie de solvants de polarite variable. L'equation de vitesse est du premier ordre vis-a-vis de chacun des deux reactif dans tous les cas. Deux types de sequences sont observees: 1. CH 3 > C 2 H 2 > n -C 3 H 7 > iso-C 3 H 7 , une sequence sterique en milieu “polaire” 2. CH 3 2 H 5 > n -C 3 H 7 3 H 7 , une sequence montrant une contribution accrue des effets inductifs, dans des solvans “peu polaires...
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#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
#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
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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 4
#2Yves Tondeur (ULB: Université libre de Bruxelles)H-Index: 7
Stannylamines, ‐phosphines and ‐arsines are shown to be configurationally stable within the NMR time‐scale, even in the presence of a strong nucleophile. The configurational stability of triorganotin hydrides and the configurational unstability of triorganotin halide has been checked. Copyright © 1975 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 38
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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#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
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Abstract Diastereotopic nonequivalence is described for molecules of the type R′Me 2 -SnCHY(CH 3 ) (with YC 2 H 5 , C 6 H 5 and with various R′ groups), for meso -R″ 2 Sn(CHYCH 3 ) 2 (with R″CH 3 , CH 2 C 6 H 5 ) and for diastereoisomers such as Me 4- n - Sn(CHZCH 3 ) n [ZEt, Pr; n 2,3] and Me-i-Pr-cyclo-HexSnCH(CH 3 ) (C 6 H 5 ).
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Abstract The trimethylchlorosilane/magnesium/hexamethylphosphoric triamide system reacts with methyl benzoate to lead to an O - and C -silylated mixed ketal, which under hydrolysis easily gives benzoyltrimethylsilane (new preparative method of this compound), but which in basic media is converted to an unexpected siloxanic isomer. Under the same conditions trimethylsilyl benzoate gives, after hydrolysis, an α- C -disilylated alcohol.
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Publisher Summary This chapter deals with turnstile rearrangement and peudorotation in the permutational isomerization of pentavalent phosphorous compounds. The phosphoranes are derivatives of the pentahydride of phosphorus, in which the five ligands are covalently bonded to phosphorus. The stereochemistry of pentavalent phosphorus relates to the trigonal bipyramid, just as that of tetravalent carbon relates to the tetrahedron. X-Ray crystallographic analysis provides details of the static molec...
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