Computational study and molecular orbital analysis of NMR shielding, spin-spin coupling, and electric field gradients...

(195)Pt, (14)N, and (15)N NMR data for five azido (N(3)(-)) complexes are studied using relativistic density functional theory (DFT). Good agreement with experiment is obtained for Pt and N chemical shifts as well as Pt-N J-coupling constants. Calculated (14)N electric field gradients (EFGs) reflect experimentally observed trends for the line broadening of azido (14)N NMR signals. A localized molecular orbital analysis of the nitrogen EFGs and chemical shifts is performed to explain some interesting trends seen experimentally and in the first-principles calculations: (i) (14)N NMR signals for the Pt-coordinating (N(α)) nuclei in the azido ligands are much broader than for the central (N(β)) or terminal (N(γ)) atoms. The N(β) signals are particularly narrow; (ii) compared to N(γ), the N(α) nuclei are particularly strongly shielded; (iii) N(β) nuclei have much larger chemical shifts than N(α) and N(γ) ; and (iv) The Pt-N(α) J-coupling constants are small in magnitude when considering the formal sp hybridization of N(α). It is found that for N(α) a significant shielding reduction due to formation of the dative N(α)-Pt bond is counterbalanced by an increased shielding from spin-orbit (SO) coupling originating at Pt. Upon coordination, the strongly delocalized π system of free azide localizes somewhat on N(β) and N(γ). This effect, along with rehybridization at N(α) upon bond formation with Pt, is shown to cause a deshielding of N(γ) relative to N(α) and a strong increase of the EFG at N(α). The large 2p character of the azide σ bonds is responsible for the particularly high N(β) chemical shifts. The nitrogen s-character of the Pt-N(α) bond is low, which is the reason for the small J-coupling. Similar bonding situations are likely to be found in azide complexes with other transition metals.