Characterization of a Reactive Rh2 Nitrenoid by Crystalline Matrix Isolation Academic Article uri icon

abstract

  • The fleeting lifetimes of reactive intermediates in C-H functionalization chemistry often prevent their direct characterization. For example, the critical nitrenoid intermediates that mediate Rh2-catalyzed C-H amination have eluded characterization for more than 40 years. In the absence of structural characterization of these species, methodological development is often computationally guided. Here we report the first X-ray crystal structure of a reactive Rh2 nitrenoid, enabled by N2 elimination from an organic azide ligand within a single-crystal matrix. The resulting high-resolution structure displays metrical parameters consistent with a triplet nitrene complex of Rh2. The demonstration of facile access to reactive metal nitrenoids within a crystalline matrix provides a platform for structural characterization of the transient species at the heart of C-H functionalization.

author list (cited authors)

  • Das, A., Chen, Y., Reibenspies, J. H., & Powers, D. C.

complete list of authors

  • Das, Anuvab||Chen, Yu-Sheng||Reibenspies, Joseph H||Powers, David C

publication date

  • January 1, 2019 11:11 AM