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Download fileHeptadentate, Octadentate, Or Even Nonadentate? Denticity in the Unexpected Formation of an All-Carbon Donor-Atom Ligand in RhIII(Cp*)(Anthracenyl-NHC) Complexes
journal contribution
posted on 2021-06-08, 12:05 authored by Betty
Y. T. Lee, Andrew D. Phillips, Muhammad Hanif, Kelvin K. H. Tong, Tilo Söhnel, Christian G. HartingerInvestigations
on incorporating an N-flanking
anthracenyl moiety to [Rh(Cp*)(NHC)Cl2] complexes surprisingly
led to the formation of an intramolecular C–C bond between
the Cp* and anthracenyl moieties, with additional auxiliary interactions
between the metal and the anthracenyl ring system. In silico modeling supports a reaction mechanism whereby Rh(η4-tetramethylfulvene) intermediates undergo metallocycloaddition and
the abstraction of a chlorido ligand, affording unique cationic complexes
that feature Rh centers coordinated by a nonadentate ligand with exclusively
carbon donor atoms. Some Rh–C interactions were extremely weak
but nevertheless exhibited covalent bonding character. These weak
Rh–C interactions were readily displaced by stronger electron
donors, and the nonadentate ligand reverted to the heptadentate coordination
mode observed in the intermediate. As far as we are aware, this study
provides the first conclusive evidence of complexes bearing a single
nonadentate κ9-coordinating ligand that features
only carbon donors bound to a metal center.