ISSN:
0749-1581
Keywords:
Paramagnetic NMR
;
Natural abundance 2H NMR
;
2H signal narrowing
;
2H isotope effect
;
EHMO calculation
;
Chemistry
;
Analytical Chemistry and Spectroscopy
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The methylated metallocenes (MeCp)2M with M = V, Cr, Mn, Co, Ni (1-5) were investigated by 1H and 2H NMR spectroscopy at natural abundance. The 2H NMR signals are narrower by a factor of up to 30 compared with the corresponding 1H NMR signals, thus establishing an inexpensive method and a general improvement of the NMR spectra of paramagnetic π-complexes. This has allowed the resolution of the signal splitting of Cp deuterons of 1 and 5 which could not be observed earlier in the 1H NMR spectra. The origin of the small (1 and 5) and large (2-4) signal splittings is discussed and related to an extended Hückel calculation. The relative magnitude of the signal splitting is reproduced, but the signal assignment had to be deduced from 13C NMR results. Primary isotope shifts of up to 4.0 ppm were found for 1, 2, 4 and 5. The much higher values for 3 (up to 16.6 ppm) reflect the combined influence of the intrinsic isotope shift and the isotope effect on the spin crossover.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/mrc.1260310103
Permalink
