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Remarkably Large 15N, 13C and 18O Isotope NMR Shifts of the Mono-coordinate Phosphorus Atoms in the Compounds (Me3 Si)iPrNCP, K+[iPrNCP]-and KOCP · 2 DME (DME = 1,2-Dimethoxyethane)
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June 2, 2014
The 31P and 13C NMR spectra of the heteroatom-substituted λ3-phosphaalkynes (Me3Si)- iPrNCP (1), K+ [iPrNCPl- (2) and KOCP · 2 DME (3) are described (Me = methyl; iPr = isopropyl). In addition,15N NMR data of 1 and 2 as well as further NMR results of all accessible nuclei of 1 to 3 are reported. The absolute values of the coupling constants 1J(31P13C) of 1, 2 and 3, 18.2, 45.7 and 57.2 Hz, respectively, are considerably different; the geminal coupling constants 2J( 31P15N) of the first two compounds show a decrease in the reverse order, 15.1 and 3.3 Hz. 13C, 29Si,15N, and 18O isotope effects on the nuclear shielding of the 31P nucleus in the non isotope-enriched compounds 1, 2 or 3 are presented and discussed. The [mono-13C]isotopomers of 1, 2 and 3 exhibit extremely negative 31P13C one-bond isotope shifts varying from -211 to -223 ppb. Remarkably, for 1 and 2 large two-bond 31P15N isotope shifts of -32 and -84 ppb, respectively, are observed. An unexpectedly large two-bond 31P180 isotope effect of -124 ppb was assigned to the [mono-180]isotopomer of compound 3. A three-bond 31P13C isotope shift of -27 ppb was found in 2.
Received: 2000-11-13
Published Online: 2014-6-2
Published in Print: 2001-2-1
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung
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