Structural Insights from ⁵⁹ Co Solid-State NMR Experiments on Organocobalt(I) Catalysts

A series of fumarate-based organocobalt(I) [CoCp(CO)(fumarate)] catalysts is synthesized and characterized by X-ray crystallography, multinuclear (¹³ C and ⁵⁹ Co) solid-state NMR spectroscopy, and ⁵⁹ Co NQR spectroscopy. Given the dearth of ⁵⁹ Co solid-state NMR studies on Co^I compounds, the present work constitutes the first systematic characterization of the ⁵⁹ Co electric field gradient and chemical shift tensors for a series of cobalt complexes in this oxidation state. Using X-ray crystallography, the molecular geometry about the Co^I centre is found to be nearly identical in all compounds studied herein. Owing to the ⁵⁹ Co nucleus' large chemical shift range, solid-state NMR experiments are found to be able to detect small structural differences between the individual organocobalt(I) compounds. With the aid of density functional theory calculations on these complexes, it is shown that the ⁵⁹ Co chemical shift anisotropy and the ⁵⁹ Co quadrupolar coupling constant are both extremely sensitive gauges of the Fu-Co-Cp bond angle, providing a link between these ⁵⁹ Co NMR observables and the catalysts' structures.