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C-C bond formation and related reactions at the CNC backbone in (smif)FeX (smif = 1,3-di-(2-pyridyl)-2-azaallyl): Dimerizations, 3 + 2 cyclization, and nucleophilic attack; Transfer hydrogenations and alkyne trimerization (X = N(TMS)2, dpma = (Di-(2-pyridyl-methyl)-amide))

Frazier BA, Williams VA, Wolczanski PT, Bart SC, Meyer K, Cundari TR, Lobkovsky EB (2013)

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Publication Type: Journal article, Original article

Publication year: 2013

Journal

Original Authors: Frazier B.A., Williams V.A., Wolczanski P.T., Bart S.C., Meyer K., Cundari T.R., Lobkovsky E.B.

Publisher: American Chemical Society

Book Volume: 52

Pages Range: 3295-3312

Journal Issue: 6

DOI: 10.1021/ic302783y

Abstract

Molecular orbital analysis depicts the CNC backbone of the smif (1,3-di-(2-pyridyl)-2-azaallyl) ligand as having singlet diradical and/or ionic character where electrophilic or nucleophilic attack is plausible. Reversible dimerization of (smif)Fe{N(SiMe)} (1) to [{(MeSi)N}Fe](μ-κ, κ-N,py-smif,smif) (2) may be construed as diradical coupling. A proton transfer within the backbone-methylated, and o-pyridine-methylated smif of putative (MeMesmif)FeN(SiMe) (8) provides a route to [{(MeSi)N}Fe](μ- κ,κ-N,py,C-(Me, CH,Me(smif)H)) (9). A 3 + 2 cyclization of ditolyl-acetylene occurs with 1, leading to the dimer [{2,5-di(pyridin-2-yl)-3,4-di-(p-tolyl-2,5-dihydropyrrol-1-ide)}FeN(SiMe )] (11), and the collateral discovery of alkyne cyclotrimerization led to a brief study that identified Fe(N(SiMe )(THF) as an effective catalyst. Nucleophilic attack by (smif)Fe (13) on BuNCO and (2,6-Pr CH)NCO afforded (RNHCO-smif)Fe (14a, R = Bu; 14b, 2,6-PrCH). Calculations suggested that (dpma)Fe (15) would favorably lose dihydrogen to afford (smif)Fe (13). H-transfer to alkynes, olefins, imines, PhNNPh, and ketones was explored, but only stoichiometric reactions were affected. Some physical properties of the compounds were examined, and X-ray structural studies on several dinuclear species were conducted. © 2013 American Chemical Society.

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APA:

Frazier, B.A., Williams, V.A., Wolczanski, P.T., Bart, S.C., Meyer, K., Cundari, T.R., & Lobkovsky, E.B. (2013). C-C bond formation and related reactions at the CNC backbone in (smif)FeX (smif = 1,3-di-(2-pyridyl)-2-azaallyl): Dimerizations, 3 + 2 cyclization, and nucleophilic attack; Transfer hydrogenations and alkyne trimerization (X = N(TMS)2, dpma = (Di-(2-pyridyl-methyl)-amide)). Inorganic Chemistry, 52(6), 3295-3312. https://dx.doi.org/10.1021/ic302783y

MLA:

Frazier, Brenda A., et al. "C-C bond formation and related reactions at the CNC backbone in (smif)FeX (smif = 1,3-di-(2-pyridyl)-2-azaallyl): Dimerizations, 3 + 2 cyclization, and nucleophilic attack; Transfer hydrogenations and alkyne trimerization (X = N(TMS)2, dpma = (Di-(2-pyridyl-methyl)-amide))." Inorganic Chemistry 52.6 (2013): 3295-3312.

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