Conjugation in phosphabutadienes: ab initio investigation and NMR spectral manifestation

Rozhenko AB, Schoeller W, Povolotskii MI (2000)
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 498(1-3): 1-20.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
Download
Es wurde kein Volltext hochgeladen. Nur Publikationsnachweis!
Autor/in
; ;
Abstract / Bemerkung
The 2,3-diphospha- and 2-aza-3-phosphabuta- 1,3-dienes (H3Si)(2)C=P-X=CYY' (1 X= P, Y, Y' = NH2; 2 X = P, Y, Y' = H; 7 X = N, Y, Y' = NH2; 8 X = N, Y, Y' = H; 9 X = N, Y = NH2 (E-), Y' = H (Z-); 10 X = N, Y = H (E-), Y' = NH2 (Z-)) as well as the isostructural butadienes (H3Si)(2)C=CH-CH=CY2 (5 Y = NH2; 6 Y = H), the symmetrical diphosphabutadienes (H3Si)(2)C=P-P=C(SiH3), (3) and (H2N)(2)C=P-P=C(NH2)(2) (4), were explored with ab initio calculations. The analysis of the geometrical parameters, natural atomic charges and Wiberg bond indices, rotational energy surfaces and energies of the isodesmic reactions shows an essential contribution of pi-electron delocalization for the model butadienes 1, 5, 7, 9, and 10. On the contrary, in 2, 3 and 4 the stabilization due to the conjugation effects is negligible or in general absent. The NMR chemical shielding values, calculated for 1-10 with the GIAO procedure at the RHF/6-311 + G(d,p) level, as well as those published for the electron-rich butadienes (Me3Si)(2)C=P-X=C(NMe2)(2) (X = N, P), agree qualitatively with the global conception of Variation of the structural parameters and charge distribution due to the pi-electron delocalization in the molecules. (C) 2000 Elsevier Science B.V. All rights reserved.
Stichworte
isodesmic reaction; rotational energy; pi-electron delocalization; surface; phosphabutadienes; GIAO NMR chemical shift calculation
Erscheinungsjahr
2000
Zeitschriftentitel
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
Band
498
Ausgabe
1-3
Seite(n)
1-20
ISSN
0166-1280
Page URI
https://pub.uni-bielefeld.de/record/1620477

Zitieren

Rozhenko AB, Schoeller W, Povolotskii MI. Conjugation in phosphabutadienes: ab initio investigation and NMR spectral manifestation. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM. 2000;498(1-3):1-20.
Rozhenko, A. B., Schoeller, W., & Povolotskii, M. I. (2000). Conjugation in phosphabutadienes: ab initio investigation and NMR spectral manifestation. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 498(1-3), 1-20. doi:10.1016/S0166-1280(99)00206-7
Rozhenko, A. B., Schoeller, W., and Povolotskii, M. I. (2000). Conjugation in phosphabutadienes: ab initio investigation and NMR spectral manifestation. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 498, 1-20.
Rozhenko, A.B., Schoeller, W., & Povolotskii, M.I., 2000. Conjugation in phosphabutadienes: ab initio investigation and NMR spectral manifestation. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 498(1-3), p 1-20.
A.B. Rozhenko, W. Schoeller, and M.I. Povolotskii, “Conjugation in phosphabutadienes: ab initio investigation and NMR spectral manifestation”, JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, vol. 498, 2000, pp. 1-20.
Rozhenko, A.B., Schoeller, W., Povolotskii, M.I.: Conjugation in phosphabutadienes: ab initio investigation and NMR spectral manifestation. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM. 498, 1-20 (2000).
Rozhenko, AB, Schoeller, Wolfgang, and Povolotskii, MI. “Conjugation in phosphabutadienes: ab initio investigation and NMR spectral manifestation”. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 498.1-3 (2000): 1-20.