Density functional computation of 49Ti NMR chemical shifts.

49Ti chemical shifts of TiX4 (X = Cl, Br, F), TiClnMe(4-n) (n = 0-3), Ti(C5H5)2X2 (X = F, Cl, Br) and Ti(CO)6(2-) were computed, using geometries optimized with the gradient-corrected BP86 density functional, at the GIAO (gauge-including atomic orbitals)-Hartree-Fock, BPW91, and B3LYP levels. For this set of compounds, substituent effects on delta(49Ti) are reasonably well described with all methods considered; judged from mean absolute deviations from experiment, B3LYP performs best. Zero-point corrections to the delta(49Ti) values, evaluated from a perturbational approach based on vibrationally averaged effective geometries, turn out to be fairly small. Electric field gradients computed with the B3LYP functional do not correlate with trends in 49Ti NMR linewidths. Attempts are reported to correlate the delta(49Ti) values of Ti[YC(O)CHC(O)Y]2Cl2 (Y = H, Me, CF3, CN, F, Cl and Br) with the rate-limiting propagation barrier for ethylene polymerization using catalysts derived from these precursors. 2004 John Wiley & Sons, Ltd.