scholarly journals H/D exchange under mild conditions in arenes and unactivated alkanes with C6D6 and D2O using rigid, electron-rich iridium PCP pincer complexes

2020 ◽  
Vol 11 (39) ◽  
pp. 10705-10717 ◽  
Author(s):  
Joel D. Smith ◽  
George Durrant ◽  
Daniel H. Ess ◽  
Benjamin S. Gelfand ◽  
Warren E. Piers

The synthesis and characterization of an iridium polyhydride complex (Ir-H4) supported by an electron-rich PCP framework and capable of mild hydrogen/deuterium exchange catalysis is described.

2020 ◽  
Author(s):  
Joel D. Smith ◽  
George Durrant ◽  
Daniel Ess ◽  
Warren Piers

<div>The synthesis and characterization of an iridium polyhydride complex (Ir-H4)</div><div>supported by an electron-rich PCP framework is described. This complex readily loses molecular</div><div>hydrogen allowing for rapid room temperature hydrogen isotope exchange (HIE) at the hydridic</div><div>positions and the α-C-H site of the ligand with deuterated solvents such as benzene-d6, toluene-d8</div><div>and THF-d8. The removal of 1-2 equivalents of molecular H2 forms unsaturated iridium carbene</div><div>trihydride (Ir-H3) or monohydride (Ir-H) compounds that are able to create further unsaturation</div><div>by reversibly transferring a hydride to the ligand carbene carbon. These species are highly active</div><div>hydrogen isotope exchange (HIE) catalysts using C6D6 or D2O as deuterium sources for the</div><div>deuteration of a variety of substrates. By modifying conditions to influence the Ir-Hn speciation,</div><div>deuteration levels can range from near exhaustive to selective only for sterically accessible sites.</div><div>Preparative level deuterations of select substrates were performed allowing for procurement of</div><div>>95% deuterated compounds in excellent isolated yields; the catalyst can be regenerated by</div><div>treatment of residues with H2 and is still active for further reactions.</div>


2020 ◽  
Author(s):  
Joel D. Smith ◽  
George Durrant ◽  
Daniel Ess ◽  
Warren Piers

<div>The synthesis and characterization of an iridium polyhydride complex (Ir-H4)</div><div>supported by an electron-rich PCP framework is described. This complex readily loses molecular</div><div>hydrogen allowing for rapid room temperature hydrogen isotope exchange (HIE) at the hydridic</div><div>positions and the α-C-H site of the ligand with deuterated solvents such as benzene-d6, toluene-d8</div><div>and THF-d8. The removal of 1-2 equivalents of molecular H2 forms unsaturated iridium carbene</div><div>trihydride (Ir-H3) or monohydride (Ir-H) compounds that are able to create further unsaturation</div><div>by reversibly transferring a hydride to the ligand carbene carbon. These species are highly active</div><div>hydrogen isotope exchange (HIE) catalysts using C6D6 or D2O as deuterium sources for the</div><div>deuteration of a variety of substrates. By modifying conditions to influence the Ir-Hn speciation,</div><div>deuteration levels can range from near exhaustive to selective only for sterically accessible sites.</div><div>Preparative level deuterations of select substrates were performed allowing for procurement of</div><div>>95% deuterated compounds in excellent isolated yields; the catalyst can be regenerated by</div><div>treatment of residues with H2 and is still active for further reactions.</div>


2018 ◽  
Vol 30 (2) ◽  
pp. 235-247 ◽  
Author(s):  
O. Tara Liyanage ◽  
Matthew R. Brantley ◽  
Emvia I. Calixte ◽  
Touradj Solouki ◽  
Kevin L. Shuford ◽  
...  

FEBS Journal ◽  
2009 ◽  
Vol 276 (15) ◽  
pp. 4051-4060 ◽  
Author(s):  
Anders Olofsson ◽  
Malin Lindhagen-Persson ◽  
Monika Vestling ◽  
A. Elisabeth Sauer-Eriksson ◽  
Anders Öhman

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