PT Journal
AU Bühl, M
   Peters, D
   Herges, R
TI Substituent effects on 61Ni NMR chemical shifts
SO Dalton Transactions
PY 2009
BP 6037
EP 6044
IS 30
PU Roayal Society of Chemistry
DI 10.1039/b902308a
WP https://macau.uni-kiel.de/receive/publ_mods_00000041
LA en
DE chemical shifts
SN 1477-9226
AB 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.
PI London
ER