Density-functional computation of ⁹³Nb NMR chemical shifts.
93Nb chemical shifts of [NbX6](-) (X = Cl, F, CO), [NbXCl4](-) (X = O, S), Nb2(OMe)10, Cp*2Nb(κ2-BH4), (Cp*Nb)2(µ-B2H6)2, CpNb(CO)4, and Cp2NbH3 are computed at the GIAO (gauge-including atomic orbitals)-, BPW91- and B3LYP-, and CSGT (continuous set of gauge transformations)-CAM-B3LYP, -ωB97, and -ωB97X levels, using BP86-optimized or experimental (X-ray) geometries. Experimental chemical shifts are best reproduced at the GIAO-BPW91 level when δ(93Nb) values of inorganic complexes are referenced directly relative to [NbCl6](-) and those of organometallic species are first calculated relative to [Nb(CO)6](-). An inadvertent error in the reported δ(93Nb) values of cyclopentadiene borane complexes (H. Brunner et al., J. Organomet. Chem.1992, 436, 313) is corrected. Trends in the observed 93Nb NMR linewidths for anionic niobates [Nb(CO)5](3-), [Nb(CO)5H](2-), and [Nb(CO)5(NH3)](-) are rationalized in terms of computed electric field gradients at the metal.
Bühl
Michael
M
School of Chemistry, North Haugh, University of St Andrews, St Andrews, Fife KY16 9ST, UK. buehl@st-andrews.ac.uk
Wrackmeyer
Bernd
B
D009682:Magnetic Resonance Spectroscopy / Q000592:standards; D008968:Molecular Conformation; D009556:Niobium / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D012015:Reference Standards
D009942:Organometallic Compounds; D009556:Niobium