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Title: On the use of stereodynamical effects to control cold chemical reactions: The H + D 2 ⟷ D + HD case study
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Award ID(s):
2110227 1806334
Publication Date:
Journal Name:
The Journal of Chemical Physics
Page Range or eLocation-ID:
Article No. 044305
American Institute of Physics
Sponsoring Org:
National Science Foundation
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  1. The synthesis and characterization of an iridium polyhydride complex ( Ir-H4 ) supported by an electron-rich PCP framework is described. This complex readily loses molecular hydrogen allowing for rapid room temperature hydrogen isotope exchange (HIE) at the hydridic positions and the α-C–H site of the ligand with deuterated solvents such as benzene-d 6 , toluene-d 8 and THF-d 8 . The removal of 1–2 equivalents of molecular H 2 forms unsaturated iridium carbene trihydride ( Ir-H3 ) or monohydride ( Ir-H ) compounds that are able to create further unsaturation by reversibly transferring a hydride to the ligand carbene carbon. These species are highly active hydrogen isotope exchange (HIE) catalysts using C 6 D 6 or D 2 O as deuterium sources for the deuteration of a variety of substrates. By modifying conditions to influence the Ir-Hn speciation, deuteration levels can range from near exhaustive to selective only for sterically accessible sites. Preparative level deuterations of select substrates were performed allowing for procurement of >95% deuterated compounds in excellent isolated yields; the catalyst can be regenerated by treatment of residues with H 2 and is still active for further reactions.