Sterically Crowded Σ‐ and Π‐bonded Metal Aryl Complexes

Martı́nez, Gabriel; Killion, Jack A.; Jackson, Bailey J.; Fout, Alison R.; Petel, Brittney E.; Matson, Ellen M.; Gridley, Benjamin M.; Moxey, Graeme J.; Kays, Deborah L.; Bryan, Aimee M.; Power, Philip P.; Erickson, Jeremy D.; Riparetti, Ryan D.; Blundell, Toby J.; Ramos, Ana M. Geer; Sharpe, Helen R.; Abraham, Mariham Y.; Smith, Jennifer M.; Wang, Yu‐Zhong; Robinson, Gregory H.; Saleh, Mahmoud A.; Osman, Khalid; Wehmschulte, Rudolf J.; Brennessel, William W.; Ellis, John E.; Wolf, Robert; Chakraborty, Uttam; Büschelberger, Philipp; Rödl, Christian; Wiegel, Anne‐Kathrin

doi:10.1002/9781119477822.ch4

Cited by 1 publication

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“…Ferrocenium hexafluorophosphate was synthesized following a previously reported procedure . Fe 2 Mes 4 was synthesized as previously reported . Celite 545 (J. T. Baker) was dried in a Schlenk flask for 24 h under dynamic vacuum while heating to at least 150 °C prior to use in a dry box.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis, Characterization, and the Effect of Lewis Bases on the Nuclearity of Iron Alkoxide Complexes

Gwinn,

Williams,

Latendresse

et al. 2024

Inorg. Chem.

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Inspired by the potential of alkoxides as weak-field ligands and their ability to bridge, we report herein a series of highspin iron complexes supported by a bis-alkoxide framework Ph Dbf. A diiron complex [Fe 2 ( Ph Dbf) 2 ] (1a) is obtained upon metalation of the ligand, whereas addition of substituted pyridines affords fivecoordinate mononuclear iron complexes [(R-Py) 2 Fe( Ph Dbf)] (2a− 4a, R = H, p-t Bu, p-CF 3 ). The potential for nuclearity control of the metal complexes via auxiliary ligands is highlighted by the formation of asymmetric diiron species [(p-CF 3 −Py)Fe 2 ( Ph Dbf) 2 ] (5a) and [(m-CF 3 −Py)Fe 2 ( Ph Dbf) 2 ] (6a) with trifluoromethyl substituted pyridines, while electron-rich pyridines only produced monomeric species. Electronic properties analysis via UV−vis, electron paramagnetic resonance, 57 Fe Mossbauer spectroscopy, and time-dependent density functional theory, along with redox capabilities of these complexes are reported to illustrate the effect of nuclearity on reactivity and the potential of these complexes to access higher oxidation states relevant in oxidative chemistry. Species 1a−5a, [(THF) 2 Fe( Ph Dbf)][PF 6 ] (7), [PyFe( Ph Dbf)Cl] (2b), and [Py 2 Fe( Ph Dbf)][PF 6 ] (2c) were characterized via SCXRD. Indirect evidence for the formation of dimeric Fe(III) species (1b, 5b, and 6b) is discussed.

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Section: Methodsmentioning

confidence: 99%

“… 45 Fe 2 Mes 4 was synthesized as previously reported. 46 Celite 545 (J. T. Baker) was dried in a Schlenk flask for 24 h under dynamic vacuum while heating to at least 150 °C prior to use in a dry box. Silica gel 32–63 μ (AIC, Framingham, MA) was used as received.…”

Section: Methodsmentioning

confidence: 99%