Ligand-centered redox activity: redox properties of 3d transition metal ions ligated by the weak-field tris(pyrrolyl)ethane trianion

Inorganic Chemistry
Graham T Sazama, Theodore A Betley

Abstract

First-row transition metal complexes of the tris(pyrrolyl)ethane (tpe) trianion have been prepared. The tpe ligand was found to coordinate in a uniform eta(1),eta(1),eta(1)-coordination mode to the divalent metal series as revealed by X-ray diffraction studies. Magnetic and structural characterization for complexes of the type [(tpe)M(II)(py)][Li(THF)(4)] (M: Mn, Fe, Co, Ni) reveal each divalent ion to be high-spin and have a distorted trigonal-monopyramidal geometry in the solid state. The pyridine ligand binds significantly canted from the molecular C(3) axis due to a stabilizing pi-stacking interaction with a ligand mesityl substituent. Cyclic voltammetry on the [(tpe)M(II)(py)](-) series reveals a common irreversible oxidation pathway that is entirely ligand-based, invariant to the divalent metal bound. This latter observation indicates that fully populated ligand-based orbitals from the tpe construct are energetically most accessible in the electrochemical experiments, akin to their dipyrromethane analogues. Chemical oxidation of [(tpe)Fe(II)(py)](-) yields a product in which the ligand has dissociated one pyrrole (following tpe oxidation and H-atom abstraction) and binds a second equivalent of pyridine to form the neutral...Continue Reading

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Citations

Jul 23, 2011·Inorganic Chemistry·Jaime A FloresKenneth G Caulton
Aug 6, 2013·Inorganic Chemistry·Nikolay P TsvetkovKenneth G Caulton
Dec 11, 2013·Inorganic Chemistry·Graham T Sazama, Theodore A Betley
Apr 19, 2011·Chemical Communications : Chem Comm·John S HartJason B Love
Dec 23, 2014·The Journal of Physical Chemistry. B·Toshihiko MandaiMasayoshi Watanabe
Jan 5, 2012·Journal of the American Chemical Society·Julian P BigiChristopher J Chang
Dec 15, 2010·Journal of the American Chemical Society·W Hill HarmanChristopher J Chang
Sep 18, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Serhii TretiakovMarc-Etienne Moret
May 5, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·David M GranumMark P Mehn
Aug 24, 2021·Journal of the American Chemical Society·Charles WinslowJonathan Rittle

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