Iron Complexes Derived from {nacnac-(CH(2)py)(2)}(-) and {nacnac-(CH(2)py)(CHpy)}(n) Ligands: Stabilization of Iron(II) via Redox Noninnocence

Williams VA, Wolczanski PT, Sutter J, Meyer K, Lobkovsky EB, Cundari TR (2014)

Publication Status: Published

Publication Type: Journal article

Publication year: 2014

Journal

Inorganic Chemistry American Chemical Society

Publisher: American Chemical Society

Book Volume: 53

Pages Range: 4459-4474

DOI: 10.1021/ic5001123

Abstract

Nacnac-based tetradentate chelates, {nacnac-(CH(2)py)(2)} ({nn(PM)(2)}(-)) and {nacnac-(CH(2)py)(CHpy)}(n) ann(PM)(PI)}(n)) have been investigated in iron complexes. Treatment of Fe{N(TMS)(2)}(2)(THF) with {nn(PM)(2)}H afforded {nn(PM)(2)}FeN(TMS)(2) [1-N(TMS)(2)], which led to {nn(PM)(2)}FeCl (1-Cl) from HCl and to {nn(PM)(2)}FeN3 (1-N-3) upon salt metathesis. Dehydroamination of 1-N(TMS)(2) was induced by L (L = PMe3, CO) to afford {nn(PM)(PI)}Fe(PMe3)(2) [2-(PMe3)(2)] and {nn(PM)(PI)}FeCO (3-CO). Substitution of 2-(PMe3)(2) led to {nn(PM)(PI)}Fe(PMe3)CO [2-(PMe3)CO], and exposure to a vacuum provided {nn(PM)(PI)}Fe(PMe3) (3-PMe3). Metathesis routes to {nn(PM)(PI)}FeL2 (2-L-2; L = PMe3, PMe2Ph) and {nn(PM)(PI)}FeL (3-L; L = PMePh2, PPh3) from [inn(PM)(PI)}(2-)]Li-2 and FeBr2(THF)(2) in the presence of L proved feasible, and 1e(-) and 2e(-) oxidation of 2-(PMe3)(2) afforded 2(+)-(PMe3)(2) and 2(2+)-(PMe3)(2) salts. Mossbauer spectroscopy, structural studies, and calculational assessments revealed the dominance of iron(II) in both high-spin (1-X) and low-spin (2-L-2 and 3-L) environments, and the redox noninnocence (RNI) of {nn(PM)(PI)}(n) [2-L-2, 3-L, n = 2-; 2(+)-(PMe3)(2), n = 1; 2(2+)-(PMe3)(2), n = 0]. A discussion regarding the utility of RNI in chemical reactivity is proffered.

Authors with CRIS profile

Jörg Sutter Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Cornell University US United States (USA) (US) University of North Texas (UNT) US United States (USA) (US)

How to cite

APA:

Williams, V.A., Wolczanski, P.T., Sutter, J., Meyer, K., Lobkovsky, E.B., & Cundari, T.R. (2014). Iron Complexes Derived from {nacnac-(CH(2)py)(2)}(-) and {nacnac-(CH(2)py)(CHpy)}(n) Ligands: Stabilization of Iron(II) via Redox Noninnocence. Inorganic Chemistry, 53, 4459-4474. https://dx.doi.org/10.1021/ic5001123

MLA:

Williams, Valerie A., et al. "Iron Complexes Derived from {nacnac-(CH(2)py)(2)}(-) and {nacnac-(CH(2)py)(CHpy)}(n) Ligands: Stabilization of Iron(II) via Redox Noninnocence." Inorganic Chemistry 53 (2014): 4459-4474.

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