P-31 SOLID-STATE NMR-STUDY OF IMINOPHOSPHINES - INFLUENCE OF ELECTRONIC-STRUCTURE AND CONFIGURATION OF THE DOUBLE-BOND ON PHOSPHORUS SHIELDING

GUDAT D, HOFFBAUER W, NIECKE E, Schoeller W, FLEISCHER U, KUTZELNIGG W (1994)
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 116(16): 7325-7331.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
Download
Es wurden keine Dateien hochgeladen. Nur Publikationsnachweis!
Autor*in
GUDAT, D; HOFFBAUER, W; NIECKE, E; Schoeller, WolfgangUniBi; FLEISCHER, U; KUTZELNIGG, W
Abstract / Bemerkung
The principal elements of the P-31 nuclear magnetic shielding tensors of iminophosphines of the type R-P double bond N-aryl (aryl = C(6)H(2)tBu(3); R = tBU, Ph(3)Sn(tBu)N, aryl-N double bond P-(tBu)N, aryl-NH, aryl-N double bond P-(adamantyl)N, Ph(2)N, carbazolyl, tBu(2)C double bond N, iminofluorenyl, Cl, Pr, I; 5-16) are determined from high-resolution solid-state MAS (magic angle spinning) NMR spectra. Comparison of the data with the results of IGLO calculations on shielding tensors of model compounds is used to assign the orientation of the principal axes system in the molecular frame. The observed shieldings can be correlated with structural features of the compounds. In (E)-configured alkyl- and amino-iminophosphines, the component at high field (delta(33)) is approximately perpendicular to the RPN plane and the low-field component (delta(11)) is in this plane and close to the P-R bond. Introduction of a-donor substituents (R'N-2) at phosphorus produces large increases in delta(11), which can be related to corresponding changes in the n-pi* electronic transition energies. A similar effect is found for a change of the double-bond geometry from (E)- to (Z)-configuration. Electronegative halogen substituents (Cl, Br) give rise to a further substantial increase in the tenser component at high field, delta(33). Furthermore, a change of the orientation of the principal axes system in the molecular frame occurs, with delta(33) being aligned close to the P,N bond axis and the intermediate component, delta(22), perpendicular to the RPN plane, A discussion of these effects is given in terms of partial triple-bond character for the P,N bond. The shape of the shielding tenser of the iodo compound (16) suggests that the electronic environment of the P,N moiety is similar to other systems containing a genuine triple bond, The unique difference between the isotropic chemical shifts in the solid state and in solution (Delta delta 118 ppm) in this case indicates that this phenomenon is confined to the solid state and can be attributed to the substantial polarization of the P,I bond, which is a consequence of the observed intermolecular association.
Erscheinungsjahr
1994
Zeitschriftentitel
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Band
116
Ausgabe
16
Seite(n)
7325-7331
ISSN
0002-7863
Page URI
https://pub.uni-bielefeld.de/record/1643036

Zitieren

GUDAT D, HOFFBAUER W, NIECKE E, Schoeller W, FLEISCHER U, KUTZELNIGG W. P-31 SOLID-STATE NMR-STUDY OF IMINOPHOSPHINES - INFLUENCE OF ELECTRONIC-STRUCTURE AND CONFIGURATION OF THE DOUBLE-BOND ON PHOSPHORUS SHIELDING. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 1994;116(16):7325-7331.
GUDAT, D., HOFFBAUER, W., NIECKE, E., Schoeller, W., FLEISCHER, U., & KUTZELNIGG, W. (1994). P-31 SOLID-STATE NMR-STUDY OF IMINOPHOSPHINES - INFLUENCE OF ELECTRONIC-STRUCTURE AND CONFIGURATION OF THE DOUBLE-BOND ON PHOSPHORUS SHIELDING. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 116(16), 7325-7331. https://doi.org/10.1021/ja00095a041
GUDAT, D, HOFFBAUER, W, NIECKE, E, Schoeller, Wolfgang, FLEISCHER, U, and KUTZELNIGG, W. 1994. “P-31 SOLID-STATE NMR-STUDY OF IMINOPHOSPHINES - INFLUENCE OF ELECTRONIC-STRUCTURE AND CONFIGURATION OF THE DOUBLE-BOND ON PHOSPHORUS SHIELDING”. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 116 (16): 7325-7331.
GUDAT, D., HOFFBAUER, W., NIECKE, E., Schoeller, W., FLEISCHER, U., and KUTZELNIGG, W. (1994). P-31 SOLID-STATE NMR-STUDY OF IMINOPHOSPHINES - INFLUENCE OF ELECTRONIC-STRUCTURE AND CONFIGURATION OF THE DOUBLE-BOND ON PHOSPHORUS SHIELDING. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 116, 7325-7331.
GUDAT, D., et al., 1994. P-31 SOLID-STATE NMR-STUDY OF IMINOPHOSPHINES - INFLUENCE OF ELECTRONIC-STRUCTURE AND CONFIGURATION OF THE DOUBLE-BOND ON PHOSPHORUS SHIELDING. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 116(16), p 7325-7331.
D. GUDAT, et al., “P-31 SOLID-STATE NMR-STUDY OF IMINOPHOSPHINES - INFLUENCE OF ELECTRONIC-STRUCTURE AND CONFIGURATION OF THE DOUBLE-BOND ON PHOSPHORUS SHIELDING”, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 116, 1994, pp. 7325-7331.
GUDAT, D., HOFFBAUER, W., NIECKE, E., Schoeller, W., FLEISCHER, U., KUTZELNIGG, W.: P-31 SOLID-STATE NMR-STUDY OF IMINOPHOSPHINES - INFLUENCE OF ELECTRONIC-STRUCTURE AND CONFIGURATION OF THE DOUBLE-BOND ON PHOSPHORUS SHIELDING. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 116, 7325-7331 (1994).
GUDAT, D, HOFFBAUER, W, NIECKE, E, Schoeller, Wolfgang, FLEISCHER, U, and KUTZELNIGG, W. “P-31 SOLID-STATE NMR-STUDY OF IMINOPHOSPHINES - INFLUENCE OF ELECTRONIC-STRUCTURE AND CONFIGURATION OF THE DOUBLE-BOND ON PHOSPHORUS SHIELDING”. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 116.16 (1994): 7325-7331.
Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®
Suchen in

Google Scholar