N-heterocyclic phosphenium/phosphido (NHP+/NHP-) ligands, isolobal analogues of NHC’s, have been shown to be redox active, with the ability to change from a planar geometry if in the NHP+ state to a pyramidal geometry in the NHP- state akin to nitrosyl ligands (NO+/NO-). Our group has shown that incorporating an NHP+/- fragment into a PPP pincer ligand framework destabilizes the ground state singlet of the NHP+ state, facilitating reduction and rehybridization to the NHP- state. The cobalt(I) complex (PPP)CoPMe3 was shown to undergo metal-ligand cooperative reactions with E-H bonds (E = H, O, S) but the oxidation state of cobalt remains somewhat ambiguous without the solid-state structure from single crystal X-ray diffraction. To provide more insight, we have synthesized and structurally characterized several rhodium complexes with the NHP- containing pincer ligand PPP and identified them as NHP- or NHP+ complexes by analyzing the structural parameters as well as through density functional theory (DFT) and natural bond orbital (NBO) calculations. Preliminary reactivity of the rhodium complexes with the S-H bond of thiophenol has been explored and compared to that of (PPP)CoPMe3.

Synthesis, characterization, and reactivity of several rhodium complexes of an NHP-containing pincer ligand

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.