Single-Crystal to Single-Crystal Transformations: Stepwise CO2 Insertions into Bridging Hydrides of [(NHC)CuH]2 Complexes
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 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.
- Publication:
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Angewandte Chemie
- Pub Date:
- July 2023
- DOI:
- Bibcode:
- 2023AngCh.135E4648P