Nitrogen-15 n.m.r. characterization of bent and linear nitrosyl ligands in the solid state by cross-polarisation magic-angle-spinning spectroscopy of complexes of ruthenium

Nitrogen NMR Spectroscopy of Metal Nitrosyls and Related Compounds

“…This isotope effect is observable because of large differences in stretching frequency and nitrogen shift in linear and bent nitrosyls, effects of the lone pair on the bent nitrogen. The temperature-dependence of the equilibrium isotope effect and the 15 N shifts in solution and the solid (described in section VI) show that a trigonal-bipyramidal structure with two linear nitrosyls probably contributes to the fluxions in solution. , …”

“…The temperature-dependence of the equilibrium isotope effect and the 15 N shifts in solution and the solid (described in section VI) show that a trigonal-bipyramidal structure with two linear nitrosyls probably contributes to the fluxions in solution. 46,101…”

“…The first measurement of a nitrogen tensor in a metal complex was of [RuCl( 15 NO) 2 (PPh 3 ) 2 ][BF 4 ], which has one linear and one bent nitrosyl in the solid state 101 and shows fast bent-linear fluxionality in solution. 46 The evidence of the nitrogen shifts in the solid state and in solution, showing a deshielding of ca.…”

Nitrogen-15 NMR Study of Solid Cobaloximes Containing 15N-Labeled Pyridine and Aniline

“…Results are compared with those recently reported for the free pyridine- 15 N ligand . A large number of nitrogen CS tensors in a variety of organic and inorganic complexes have been reported in the literature. , More specifically, there have been several accounts of nitrogen CS tensors of nuclei directly coordinated to transition metals. − Recent reports include nitrogen CS tensors in tetraphenylporphyrin complexes by Grant and co-workers, and in nitrosoarene−metal complexes and metalloporphyrins by Oldfield et al Ab initio calculations of nitrogen shielding tensors have also been conducted on such systems by Oldfield and co-workers, , as well as de Dios et al Though nitrogen CS tensor orientations are available from ab initio calculations, we are aware of only one transition-metal compound where the nitrogen chemical shift tensor has been inferred from experiment …”

The Preparation, Structural Characteristics, and Physical Chemical Properties of Metal-Nitrosyl Complexes

“…Nitrogen-15 solid-state NMR of [RuCl(NO) 2 (PPh 3 ) 2 ](BF 4 ) using high-resolution cross-polarization magic-angle spinning (CP/MAS) also showed a large chemical shift anisotropy for the bent as compared with the linear nitrosyl ligand [129]. …”