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 CO 2 into [(NHC)CuH] 2 without complete dissociation of the dimer. The first CO 2 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‐O 2 CH)(μ‐H). A second CO 2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐1,1‐O 2 CH), 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, vol. 135, no. 30, Jun. 2023. https://doi.org/10.1002/ange.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, 135(30). https://doi.org/10.1002/ange.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 135, no. 30 (2023), https://doi.org/10.1002/ange.202304648
@article{osti_1985197,
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 = {Abstract 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 CO 2 into [(NHC)CuH] 2 without complete dissociation of the dimer. The first CO 2 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‐O 2 CH)(μ‐H). A second CO 2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐1,1‐O 2 CH), 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/ange.202304648},
url = {https://www.osti.gov/biblio/1985197},
journal = {Angewandte Chemie},
issn = {ISSN 0044-8249},
number = {30},
volume = {135},
place = {Germany},
publisher = {Wiley Blackwell (John Wiley & Sons)},
year = {2023},
month = {06}}
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 373, Issue 2037https://doi.org/10.1098/rsta.2014.0187