High-resolution gas phase measurements of 1H NMR spectra at 400 MHz and atmospheric pressure of seven small hydrocarbons are presented. The developed new method and the experimental set-up are described. Ab initio GIAO MO calculations of 1H and 13C NMR absolute shieldings on the HF, MP2 and B3LYP levels using 25 standard gaussian basis sets are reported for these hydrocarbons, based on experimental re distances. The measured gas phase 1H chemical shifts have been converted to an absolute σ0 shielding scale by use of the literature shielding of methane. These and gas phase 13C literature values have been transferred with literature ZPV data to estimated σeexp shieldings which are used to evaluate the basis set dependence of the calculated σe shieldings utilizing linear least squares regressions. Exponential extrapolations of Dunning basis set calculations allow the determination of basis set limits for 1H and 13C shieldings. 1H and 13C chemical shifts have been derived from the HF calculated shieldings with shieldings of TMS which has been geometry optimized and GIAO calculated in each basis. Standard deviations (esd) as low as 0.09 ppm for 1H and 0.76 ppm for 13C calculations have been obtained.The statistically best basis set for simultaneous calculation of 1H and 13C absolute shieldings or relative shifts is 6-311G* within the HF and B3LYP methods. Aiming for highest accuracy and precision, 1H and 13C have to be treated separately. In this case, best results are obtained using MP2/6-311G** or higher for 1H shieldings and MP2/cc-pVTZ for 13C shieldings.

Solid-state nuclear magnetic resonance (NMR) spectroscopy is employed for the first time on urea and thiourea inclusion compounds (UICs and TICs) containing branched alkyl chains. In the present work, 2H and t3C NMR as well as X-ray diffraction studies of two selectively deuterated 2-methylhexadecanes in UIC and TIC are presented. An analysis of the derived T~ data reveals significant differences between UICs and TICs, which can be attributed to differences in the motional features of the guest species. It is found that four different motionaI contributions have to be considered, namely, chain rotation, chain wobbling, trans-gauche isomerization and methyl group rotation. 2-Methylhexadecane in UIC exists in ah almost all-trans conformation (gauche amount not more than 5%) and undergoes fast chain rotation (6-site jump process, activation energy E A = 16.7 kJ/mol). The analysis of the 2H NMR spectra of 2-methylhexadecane-l,l',2-d 7 in urea proves that the branched chain end exists in ah eclipsed conformation. The T~ data of 2-methylhexadecane-3-d 2 in thiourea can be reproduced by an overall rotation (E A = 9.8 kJ/mol) a n d a trans-gauche isomerization with torsional jumps around the C-3-C-4 bond (E A = 11.0 kJ/mol, gauche population = 15%). As for the corresponding UIC, the 2H NMR spectra of 2-methylhexadecane-l,l',2-d 7 in TIC can be only explained by the existence of an eclipsed conformation at the branched chain end.

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