Supramolecular perturbation of metal-metal bonding in cyclodextrin-encapsulated (NHC)Cu-FeCp(CO)₂ complexes.

ABSTRACT: Although secondary coordination sphere effects on catalytic active sites are widely appreciated, the influence of such interactions on (hetero)binuclear active sites has not been examined comprehensively. Here, the influence of cyclodextrin encapsulation on the (NHC)Cu-FeCp(CO)₂ moiety, which is known to be catalytically active in several transformations, is analyzed in detail. Compared to free (NHC)CuFp complexes (Fp = FeCp(CO)₂), encapsulated (NHC)CuFp complexes were found to shift from resembling Fe(0) towards having Fe(II) character according to Mössbauer and IR spectroscopies. According to DFT modeling, this change in electronic structure is correlated to pyramidalization of the Fp fragment away from a planar orientation and to disruption of semi-bridging CO inte

SUBMITTER: Mankad NP 

PROVIDER: S-EPMC12456662 | biostudies-literature | 2024 May

REPOSITORIES: biostudies-literature