Exploring Rhenium Arene Piano-Stool Chemistry with [Re(η6-C6H6)(NCCH3)3]+: A Powerful Semi-Solvated Precursor

Bolliger, Robin; Siebenmann, Lukas; Wolf, Emily; Ross, Megan; Meola, Giuseppe; Blacque, Olivier; Braband, Henrik; Alberto, Roger

doi:10.1021/acs.inorgchem.2c04346

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Bolliger, R., Siebenmann, L., Wolf, E., Ross, M., Meola, G., Blacque, O., Braband, H., & Alberto, R. (2023). Exploring Rhenium Arene Piano-Stool Chemistry with [Re(η6-C6H6)(NCCH3)3]+: A Powerful Semi-Solvated Precursor. Inorganic Chemistry, 62(10), 4227–4237. https://doi.org/10.1021/acs.inorgchem.2c04346

Abstract

Thermal treatment of the ReIII hydride complex [ReH(η5-C6H7)(η6-C6H6)]+ in CH3CN results in the formation of [Re(η6-C6H6)(NCCH3)3]+. This semi-solvated complex is remarkably stable under an ambient atmosphere and exhibits a fast CH3CN self-exchange, which facilitates substitution reactions. The CH3CN ligands are replaced by σ-donating phosphines such as trimethyl phosphine (PMe3), triphenyl phosphine (PPh3), or the bidentate 1,2-bis(diphenylphosphino)ethane (dppe) to afford [Re(η6-C6H6)(NCCH3)3–x(PR3)x]+ (if R = Me, then x = 2; if R =