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
Authors
Valentić, NatašaVitnik, Željko
Kozhushkov, Sergei I.
de Majere, Armin
Ušćumlić, Gordana
Juranić, Ivan
Article (Published version)
Metadata
Show full item recordAbstract
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.
Keywords:
[3]dendralenes / unsaturated chain carbon 13C SCS / substituent effects / reverse 13C SCS effect / MNDO-PM3 calculationsSource:
Journal of the Serbian Chemical Society, 2003, 68, 2, 67-76Publisher:
- Serbian Chemical Society, Belgrade
Institution/Community
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 .