000K  utf8
1100  $c2009
1500  eng
2050  urn:nbn:de:gbv:8-publ-413
2051  10.1039/b902308a
3000  Bühl, Michael
3010  Herges, Rainer
3010  Peters, Dietmund
4000  Substituent effects on 61Ni NMR chemical shifts  [Bühl, Michael]
4209  61 Ni chemical shifts of Ni(all-trans-cdt)L (cdt = cyclododecatriene, L = none, CO, PMe3), Ni(CO)4, Ni(C2H4)2(PMe3), Ni(cod)2 (cod = cyclooctadiene) and Ni(PX3)4 (X = Me, F, Cl) are computed at the GIAO (gauge-including atomic orbitals), BPW91, B3LYP and BHandHLYP levels, using BP86-optimised geometries and an indirect referencing scheme. For this set of compounds, substituent effects on δ(61Ni) are better described with hybrid functionals than with the pure BPW91 functional. On going from Ni(all-trans-cdt) to Ni(all-cis-cdt) the computations predict substantial shielding of the 61Ni nucleus by nearly 700 ppm, as well as a sharp increase of the electric field gradient at this position. The latter result is predicted to afford an undetectably broad 61Ni NMR line for the all-cis-cdt complex, rationalizing the apparent failure to record the NMR spectrum experimentally.
4950  https://doi.org/10.1039/b902308a$xR$3Volltext$534
4950  https://nbn-resolving.org/urn:nbn:de:gbv:8-publ-413$xR$3Volltext$534
4961  https://macau.uni-kiel.de/receive/publ_mods_00000041
5051  540
5550  chemical shifts