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• W2000208046 endingPage "27" @default.
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• W2000208046 abstract "Carbon-13 and proton coupling constants and chemical shifts are reported for di- and mono-organothallium(III) compounds of the types TlR2X and TlRX2 respectively (X = anionic species). The nature of R was varied over thirty acyclic alkyl, alicyclic alkyl and alkenyl groups. Series of related derivatives were studied to identify the major factors upon which the NMR parameters depend. Several new organothallium(III) derivatives have been synthesised. The effects of solvent and anion (X) changes on the NMR parameters are generally minor. The major factor influencing J(Tl-C) and J(Tl-H) is the number of R groups attached to thallium and the ratios of analogous couplings in TlR2X and TlRX2 are generally close to the value of 12.2 predicted on the assumption that the Fermi contact contribution dominates these coupling constants. Couplings to thallium for acyclic alkyl R groups depend on the degree of substitution in R and follow the patterns |1J| > |3J| > |2J| > |4J|, ±1J, ∓2J, ±3J for J(Tl-C) and, with few exceptions, |3J| > |2J| > |4J|, ∓2J, ±3J, ±4J for J(Tl-H). Values of 3J(Tl-H) for cyclopropyl derivatives are included with existing data to quantify Karplus-type stereochemical dependence. The values of 3J(Tl-C) and 3J(Tl-H) for TlR2X (R = cyclohexyl) suggest a preference for equatorial substitution by thallium, and a similar conclusion seems reasonable for R = cyclopentyl. |nJ(Tl-C)| in alkenyl derivatives follows the same pattern as for R = acyclic alkyl, but in contrast to alkyl derivatives, 1J and 2J have the same sign. Thallium-proton couplings 2J and 3J also have the same sign for R = alkenyl. Compounds with α,β-unsaturated R groups have very large values of 1J(Tl-C) compared to those with saturated R groups. These increases can be partly attributed to changes in hybridization at the α-carbon atom. The effects of the Cl substituent on 1J(Tl-C), 2J(Tl-H) and 1J(C-H) for Tl(ClCH2)X2 are discussed in terms of the Fermi contact contribution to these coupling constants. Substituent effects on carbon-13 chemical shifts are reported." @default.
• W2000208046 created "2016-06-24" @default.
• W2000208046 creator A5014115601 @default.
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• W2000208046 creator A5076724603 @default.
• W2000208046 date "1983-08-01" @default.
• W2000208046 modified "2023-09-23" @default.
• W2000208046 title "Carbon-13 and proton NMR parameters of mono- and di-organothallium(III) derivatives" @default.
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• W2000208046 doi "https://doi.org/10.1016/0022-328x(83)80054-0" @default.
• W2000208046 hasPublicationYear "1983" @default.
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