Relativistic DFT locates 13C NMR signal of dirhodium carbene
DFT predictions by Jochen Autschbach helped to characterize a long sought-after dirhodium donor-acceptor carbene, an important reaction intermediate in various organic transformations.
The NMR modules in ADF, by Jochen and others, was used to calculate the 13C NMR chemical shift and JRh-C coupling constant with relativistic DFT. The predicted range (δ = 218-270 ppm, JRh-C = 26.3-29.3 Hz) helped the experimentalist to locate the NMR signals (δ = 240 ppm, JRh-C = 27.3 Hz) of the highly reactive dihrodium carbene.
13C NMR shielding tensor components and LUMO of model dirhodium carbene complex
See also: teaching exercise on NMR shifts with relativistic DFT
K. P. Kornecki, J. F. Briones, V. Boyarskikh, F. Fullilove, J. Autschbach, K. E. Schrote, K. M. Lancaster, H. M. L. Davies, and J. F. Berry, Direct Spectroscopic Characterization of a Transitory Dirhodium Donor-Acceptor Carbene Complex, Science, 342, 351-354 (2013)
Key conceptsADF catalysis inorganic chemistry NMR oil & gas Relativistic DFT spectroscopy