Paramagnetic Pyrazolylborate Complexes Tp2M and Tp*2M: 1H, 13C, 11B, and 14N NMR Spectra and First-Principles Studies of Chemical Shifts.

The paramagnetic pyrazolylborates Tp2M and Tp*2M (M = Cu, Ni, Co, Fe, Mn, Cr, V) as well as [Tp2M]+ and [Tp*2M]+ (M = Fe, Cr, V) have been synthesized and their NMR spectra recorded. The 1H signal shift ranges vary from ∼30 ppm (Cu(II) and V(III)) to ∼220 ppm (Co(II)), and the 13C signal shift ranges from ∼180 ppm (Fe(III)) to ∼1150 ppm (Cr(II)). The 11B and 14N shifts are ∼360 and ∼730 ppm, respectively. Both negative and positive shifts have been observed for all nuclei. The narrow NMR signals of the Co(II), Fe(II), Fe(III), and V(III) derivatives provide resolved 13C,1H couplings. All chemical shifts have been calculated from first-principles on a modern version of Kurland-McGarvey theory which includes optimized structures, zero-field splitting, and g tensors, as well as signal shift contributions. Temperature dependence in the Fe(II) spin-crossover complex results from the equilibrium of the ground singlet and the excited quintet. We illustrate both the assignment and analysis capabilities, as well as the shortcomings of the current computational methodology.