NMR spectroscopy of the solid-state isomerization of nitrito- and nitro-pentamminecobalt(III) chloride

Cobalt-59 and nitrogen-15 NMR spectra of the nitritopentamminecobalt(III) chloride, [(NH 3 ) 5 Co-ONO]Cl 2 , and nitropentamminecobalt(III) chloride, [(NH 3 ) 5 Co-NO 2 ]Cl 2 , isomers in the solid state have been obtained at several applied magnetic field strengths. The 59 Co NMR line shapes indicate that both the cobalt nuclear quadrupolar coupling constant (C Q ) and the span of the chemical shift tensor (Ω) decrease when the complex isomerizes from [(NH 3 ) 5 Co-ONO] 2+ to [(NH 3 ) 5 Co-NO 2 ] 2+ ; C Q decreases from 23 to 10.3 MHz and Ω changes from 1650 to 260 ppm. The 15 N NMR line shapes also show a significant change in the nitrogen magnetic shielding tensor upon isomerization, with Ω decreasing from 710 to 547 ppm; also, an indirect spin-spin coupling, 1 J( 59 Co, 15 N) = 63 Hz, is observed in the 15 N NMR spectra of the nitro isomer. The NMR parameters are rationalized based on differences in the molecular structure of the two isomers. NMR spectra have also been recorded as the isomerization progresses with time and demonstrate the practicality of the technique for the study of solid-state isomerizations.Key words: 15 N, 59 Co, solid-state NMR, linkage isomerization, chemical shift tensor, electric field gradient tensor.