Mechanistic studies of substrate insertion into dimeric [(NHC)CuH]2 (NHC=N-heterocyclic carbene) complexes with two bridging hydrides have been shown to require dimer dissociation to generate transient, highly reactive (NHC)Cu-H monomers in solution. Using single-crystal to single-crystal (SC-SC) transformations, we discovered a new pathway of stepwise insertion of CO2 into [(NHC)CuH]2 without complete dissociation of the dimer. The first CO2 insertion into dimeric [(IPr*OMe)CuH]2 (IPr*OMe=N,N'-bis(2,6-bis(diphenylmethyl)-4-methoxy-phenyl)imidazole-2-ylidene) produced a dicopper formate hydride [(IPr*OMe)Cu]2(μ-1,3-O2CH)(μ-H). A second CO2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu]2(μ-1,3-O2CH)(μ-1,1-O2CH), containing two different bonding modes of the bridging formate. These dicopper formate complexes are inaccessible from solution reactions since the dicopper core cleanly ruptures to monomeric complexes when dissolved in a solvent.
Patrick, Evan A., et al. "Single-Crystal to Single-Crystal Transformations: Stepwise CO<sub>2</sub> Insertions into Bridging Hydrides of [(NHC)CuH]<sub>2</sub> Complexes." Angewandte Chemie (International Edition), vol. 62, no. 30, May. 2023. https://doi.org/10.1002/anie.202304648
Patrick, Evan A., Bowden, Mark E., Erickson, Jeremy D., Bullock, R. Morris, & Tran, Ba L. (2023). Single-Crystal to Single-Crystal Transformations: Stepwise CO<sub>2</sub> Insertions into Bridging Hydrides of [(NHC)CuH]<sub>2</sub> Complexes. Angewandte Chemie (International Edition), 62(30). https://doi.org/10.1002/anie.202304648
Patrick, Evan A., Bowden, Mark E., Erickson, Jeremy D., et al., "Single-Crystal to Single-Crystal Transformations: Stepwise CO<sub>2</sub> Insertions into Bridging Hydrides of [(NHC)CuH]<sub>2</sub> Complexes," Angewandte Chemie (International Edition) 62, no. 30 (2023), https://doi.org/10.1002/anie.202304648
@article{osti_1985167,
author = {Patrick, Evan A. and Bowden, Mark E. and Erickson, Jeremy D. and Bullock, R. Morris and Tran, Ba L.},
title = {Single-Crystal to Single-Crystal Transformations: Stepwise CO<sub>2</sub> Insertions into Bridging Hydrides of [(NHC)CuH]<sub>2</sub> Complexes},
annote = {Mechanistic studies of substrate insertion into dimeric [(NHC)CuH]2 (NHC=N-heterocyclic carbene) complexes with two bridging hydrides have been shown to require dimer dissociation to generate transient, highly reactive (NHC)Cu-H monomers in solution. Using single-crystal to single-crystal (SC-SC) transformations, we discovered a new pathway of stepwise insertion of CO2 into [(NHC)CuH]2 without complete dissociation of the dimer. The first CO2 insertion into dimeric [(IPr*OMe)CuH]2 (IPr*OMe=N,N'-bis(2,6-bis(diphenylmethyl)-4-methoxy-phenyl)imidazole-2-ylidene) produced a dicopper formate hydride [(IPr*OMe)Cu]2(μ-1,3-O2CH)(μ-H). A second CO2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu]2(μ-1,3-O2CH)(μ-1,1-O2CH), containing two different bonding modes of the bridging formate. These dicopper formate complexes are inaccessible from solution reactions since the dicopper core cleanly ruptures to monomeric complexes when dissolved in a solvent.},
doi = {10.1002/anie.202304648},
url = {https://www.osti.gov/biblio/1985167},
journal = {Angewandte Chemie (International Edition)},
issn = {ISSN 1433-7851},
number = {30},
volume = {62},
place = {United States},
publisher = {Wiley},
year = {2023},
month = {05}}
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 373, Issue 2037https://doi.org/10.1098/rsta.2014.0187