Effect of substituents on the 13C-NMR chemical shifts of 3-methylene-4-substituted-1, 4-pentadienes - Part I
Efekti supstituenata na 13C-NMR hemijska pomeranja 3-metilen-4-supstituisanih-1,4-pentadiena - deo I
Аутори
Valentić, NatašaVitnik, Željko
Kozhushkov, Sergei I.
de Majere, Armin
Ušćumlić, Gordana
Juranić, Ivan
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
The principles of linear free energy relationships were applied to the 13C substituent chemical shifts (SCS) of the carbon atoms in the unsaturated chain of 3-methylene-4-substituted-1,4-pentadienes. Correlations of the SCS with the substituent parameters of Swain and Lupton provide a mutually consistent picture of the electronic effects in these compounds. The pattern of the electronic effects can be fully rationalized by a model based on the direct transmission of substituent effects through-space (direct through-space field effects), and via conjugative interactions (resonance effects), or by substituent-induced polarization of the ¶-system in the unsaturated chain (¶-polarization effect). Semi-empirical MNDO-PM3 calculations suggest the s-cis conformation of 3-methylene-4-substituted-1,4-pentadienes as the one with minimal heat of formation.
Na 13C supstituentska hemijska pomeranja (SHP) ugljenikovih atoma u nezasićenom lancu 3-metilen-4-supstituisanih-1,4-pentadiena su primenjeni principi linearne korelacije slobodne energije. Korelacije SHP sa supstituentskim parametrima Swain-a i Lupton-a pružaju usaglašenu sliku elektronskih efekata u ovim jedinjenjima. Koncept elektronskih efekata može u potpunosti biti objašnjen modelom koji se zasniva na direktnom prenošenju efekata supstituenata kroz prostor (direktni efekti polja kroz prostor) i preko konjugacionih interakcija (rezonancioni efekti), ili putem supstituentom izazvane polarizacije ¶-sistema u nezasićenom lancu (efekti ¶-polarizacije). MNDO-PM3 semiempirijska izračunavanja upućuju na s-cis konformaciju 3-metilen-4-supstituisanih-1,4-pentadiena kao konformaciju sa minimalnom energijom obrazovanja.
Кључне речи:
[3]dendralenes / unsaturated chain carbon 13C SCS / substituent effects / reverse 13C SCS effect / MNDO-PM3 calculationsИзвор:
Journal of the Serbian Chemical Society, 2003, 68, 2, 67-76Издавач:
- Serbian Chemical Society, Belgrade
Институција/група
Tehnološko-metalurški fakultetTY - JOUR AU - Valentić, Nataša AU - Vitnik, Željko AU - Kozhushkov, Sergei I. AU - de Majere, Armin AU - Ušćumlić, Gordana AU - Juranić, Ivan PY - 2003 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/574 AB - The principles of linear free energy relationships were applied to the 13C substituent chemical shifts (SCS) of the carbon atoms in the unsaturated chain of 3-methylene-4-substituted-1,4-pentadienes. Correlations of the SCS with the substituent parameters of Swain and Lupton provide a mutually consistent picture of the electronic effects in these compounds. The pattern of the electronic effects can be fully rationalized by a model based on the direct transmission of substituent effects through-space (direct through-space field effects), and via conjugative interactions (resonance effects), or by substituent-induced polarization of the ¶-system in the unsaturated chain (¶-polarization effect). Semi-empirical MNDO-PM3 calculations suggest the s-cis conformation of 3-methylene-4-substituted-1,4-pentadienes as the one with minimal heat of formation. AB - Na 13C supstituentska hemijska pomeranja (SHP) ugljenikovih atoma u nezasićenom lancu 3-metilen-4-supstituisanih-1,4-pentadiena su primenjeni principi linearne korelacije slobodne energije. Korelacije SHP sa supstituentskim parametrima Swain-a i Lupton-a pružaju usaglašenu sliku elektronskih efekata u ovim jedinjenjima. Koncept elektronskih efekata može u potpunosti biti objašnjen modelom koji se zasniva na direktnom prenošenju efekata supstituenata kroz prostor (direktni efekti polja kroz prostor) i preko konjugacionih interakcija (rezonancioni efekti), ili putem supstituentom izazvane polarizacije ¶-sistema u nezasićenom lancu (efekti ¶-polarizacije). MNDO-PM3 semiempirijska izračunavanja upućuju na s-cis konformaciju 3-metilen-4-supstituisanih-1,4-pentadiena kao konformaciju sa minimalnom energijom obrazovanja. PB - Serbian Chemical Society, Belgrade T2 - Journal of the Serbian Chemical Society T1 - Effect of substituents on the 13C-NMR chemical shifts of 3-methylene-4-substituted-1, 4-pentadienes - Part I T1 - Efekti supstituenata na 13C-NMR hemijska pomeranja 3-metilen-4-supstituisanih-1,4-pentadiena - deo I EP - 76 IS - 2 SP - 67 VL - 68 UR - https://hdl.handle.net/21.15107/rcub_technorep_574 ER -
@article{ author = "Valentić, Nataša and Vitnik, Željko and Kozhushkov, Sergei I. and de Majere, Armin and Ušćumlić, Gordana and Juranić, Ivan", year = "2003", abstract = "The principles of linear free energy relationships were applied to the 13C substituent chemical shifts (SCS) of the carbon atoms in the unsaturated chain of 3-methylene-4-substituted-1,4-pentadienes. Correlations of the SCS with the substituent parameters of Swain and Lupton provide a mutually consistent picture of the electronic effects in these compounds. The pattern of the electronic effects can be fully rationalized by a model based on the direct transmission of substituent effects through-space (direct through-space field effects), and via conjugative interactions (resonance effects), or by substituent-induced polarization of the ¶-system in the unsaturated chain (¶-polarization effect). Semi-empirical MNDO-PM3 calculations suggest the s-cis conformation of 3-methylene-4-substituted-1,4-pentadienes as the one with minimal heat of formation., Na 13C supstituentska hemijska pomeranja (SHP) ugljenikovih atoma u nezasićenom lancu 3-metilen-4-supstituisanih-1,4-pentadiena su primenjeni principi linearne korelacije slobodne energije. Korelacije SHP sa supstituentskim parametrima Swain-a i Lupton-a pružaju usaglašenu sliku elektronskih efekata u ovim jedinjenjima. Koncept elektronskih efekata može u potpunosti biti objašnjen modelom koji se zasniva na direktnom prenošenju efekata supstituenata kroz prostor (direktni efekti polja kroz prostor) i preko konjugacionih interakcija (rezonancioni efekti), ili putem supstituentom izazvane polarizacije ¶-sistema u nezasićenom lancu (efekti ¶-polarizacije). MNDO-PM3 semiempirijska izračunavanja upućuju na s-cis konformaciju 3-metilen-4-supstituisanih-1,4-pentadiena kao konformaciju sa minimalnom energijom obrazovanja.", publisher = "Serbian Chemical Society, Belgrade", journal = "Journal of the Serbian Chemical Society", title = "Effect of substituents on the 13C-NMR chemical shifts of 3-methylene-4-substituted-1, 4-pentadienes - Part I, Efekti supstituenata na 13C-NMR hemijska pomeranja 3-metilen-4-supstituisanih-1,4-pentadiena - deo I", pages = "76-67", number = "2", volume = "68", url = "https://hdl.handle.net/21.15107/rcub_technorep_574" }
Valentić, N., Vitnik, Ž., Kozhushkov, S. I., de Majere, A., Ušćumlić, G.,& Juranić, I.. (2003). Effect of substituents on the 13C-NMR chemical shifts of 3-methylene-4-substituted-1, 4-pentadienes - Part I. in Journal of the Serbian Chemical Society Serbian Chemical Society, Belgrade., 68(2), 67-76. https://hdl.handle.net/21.15107/rcub_technorep_574
Valentić N, Vitnik Ž, Kozhushkov SI, de Majere A, Ušćumlić G, Juranić I. Effect of substituents on the 13C-NMR chemical shifts of 3-methylene-4-substituted-1, 4-pentadienes - Part I. in Journal of the Serbian Chemical Society. 2003;68(2):67-76. https://hdl.handle.net/21.15107/rcub_technorep_574 .
Valentić, Nataša, Vitnik, Željko, Kozhushkov, Sergei I., de Majere, Armin, Ušćumlić, Gordana, Juranić, Ivan, "Effect of substituents on the 13C-NMR chemical shifts of 3-methylene-4-substituted-1, 4-pentadienes - Part I" in Journal of the Serbian Chemical Society, 68, no. 2 (2003):67-76, https://hdl.handle.net/21.15107/rcub_technorep_574 .