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