A seven-coordinate iron platform and its oxo and nitrene reactivity

Han Sen Soo; Moulay T. Sougrati; Fernande Grandjean; Gary J. Long; Christopher J. Chang

doi:10.1016/j.ica.2010.12.040

A seven-coordinate iron platform and its oxo and nitrene reactivity

Han Sen Soo, Moulay T. Sougrati, Fernande Grandjean, Gary J. Long, Christopher J. Chang

Research output: Contribution to journal › Article › peer-review

29 Scopus citations

Abstract

We present a new structurally determined seven-coordinate iron platform supported by the tris(2-picolyl)amine ligand 6,6′-(pyridin-2- ylmethylazanediyl)bis(methylene)bis(N-tert-butylpicolinamide) (TPA ^2C(O)NHtBu, 3) and its reactivity with oxo and nitrene transfer agents. Oxidation of the pentagonal bipyramidal, seven-coordinate iron(II)-triflate complex [TPA^2C(O)NH ^tBuFe^II(OTf)][OTf] (4) with PhIO produces the corresponding diiron(III) μ-oxo complex [(TPA^2C(O)NH ^tBuFe^III)₂(O)][OTf]₄ (5). Mössbauer and magnetic measurements on 5 in the solid-state establish antiferromagnetic coupling between its two Fe(III) centers. Reactions of 4 with the nitrene transfer agents PhINTs (Ts = p-MeC₆H₄SO ₂) and PhINNs (Ns = p-NO₂C₆H₄SO ₂) provide the corresponding iron(III)-amide congeners [TPA ^2C(O)NHtBuFe^III(NHTs)][OTf] ₂ (6) and [TPA^2C(O)NHtBuFe ^III(NHNs)][OTf]₂ (7), respectively, affording a rare pair of isolable Fe(III)-amide compounds formed from nitrene transfer. By characterizing well-defined products in the crystalline form, derived from atom and group transfer to seven-coordinate iron, the collective data provide a starting point for the exploration of high-valent and metal-ligand multiply bonded species supported by approximate pentagonal-type ligand fields.

Original language	English (US)
Pages (from-to)	82-91
Number of pages	10
Journal	Inorganica Chimica Acta
Volume	369
Issue number	1
DOIs	https://doi.org/10.1016/j.ica.2010.12.040
State	Published - Apr 15 2011
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Keywords

High-spin iron
Mössbauer spectroscopy
Oxo and nitrene transfer
Pentagonal bipyramidal
Seven-coordinate

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10.1016/j.ica.2010.12.040

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title = "A seven-coordinate iron platform and its oxo and nitrene reactivity",

abstract = "We present a new structurally determined seven-coordinate iron platform supported by the tris(2-picolyl)amine ligand 6,6′-(pyridin-2- ylmethylazanediyl)bis(methylene)bis(N-tert-butylpicolinamide) (TPA 2C(O)NHtBu, 3) and its reactivity with oxo and nitrene transfer agents. Oxidation of the pentagonal bipyramidal, seven-coordinate iron(II)-triflate complex [TPA2C(O)NH tBuFeII(OTf)][OTf] (4) with PhIO produces the corresponding diiron(III) μ-oxo complex [(TPA2C(O)NH tBuFeIII)2(O)][OTf]4 (5). M{\"o}ssbauer and magnetic measurements on 5 in the solid-state establish antiferromagnetic coupling between its two Fe(III) centers. Reactions of 4 with the nitrene transfer agents PhINTs (Ts = p-MeC6H4SO 2) and PhINNs (Ns = p-NO2C6H4SO 2) provide the corresponding iron(III)-amide congeners [TPA 2C(O)NHtBuFeIII(NHTs)][OTf] 2 (6) and [TPA2C(O)NHtBuFe III(NHNs)][OTf]2 (7), respectively, affording a rare pair of isolable Fe(III)-amide compounds formed from nitrene transfer. By characterizing well-defined products in the crystalline form, derived from atom and group transfer to seven-coordinate iron, the collective data provide a starting point for the exploration of high-valent and metal-ligand multiply bonded species supported by approximate pentagonal-type ligand fields.",

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author = "Soo, {Han Sen} and Sougrati, {Moulay T.} and Fernande Grandjean and Long, {Gary J.} and Chang, {Christopher J.}",

year = "2011",

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doi = "10.1016/j.ica.2010.12.040",

language = "English (US)",

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pages = "82--91",

journal = "Inorganica Chimica Acta",

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T1 - A seven-coordinate iron platform and its oxo and nitrene reactivity

AU - Soo, Han Sen

AU - Sougrati, Moulay T.

AU - Grandjean, Fernande

AU - Long, Gary J.

AU - Chang, Christopher J.

PY - 2011/4/15

Y1 - 2011/4/15

N2 - We present a new structurally determined seven-coordinate iron platform supported by the tris(2-picolyl)amine ligand 6,6′-(pyridin-2- ylmethylazanediyl)bis(methylene)bis(N-tert-butylpicolinamide) (TPA 2C(O)NHtBu, 3) and its reactivity with oxo and nitrene transfer agents. Oxidation of the pentagonal bipyramidal, seven-coordinate iron(II)-triflate complex [TPA2C(O)NH tBuFeII(OTf)][OTf] (4) with PhIO produces the corresponding diiron(III) μ-oxo complex [(TPA2C(O)NH tBuFeIII)2(O)][OTf]4 (5). Mössbauer and magnetic measurements on 5 in the solid-state establish antiferromagnetic coupling between its two Fe(III) centers. Reactions of 4 with the nitrene transfer agents PhINTs (Ts = p-MeC6H4SO 2) and PhINNs (Ns = p-NO2C6H4SO 2) provide the corresponding iron(III)-amide congeners [TPA 2C(O)NHtBuFeIII(NHTs)][OTf] 2 (6) and [TPA2C(O)NHtBuFe III(NHNs)][OTf]2 (7), respectively, affording a rare pair of isolable Fe(III)-amide compounds formed from nitrene transfer. By characterizing well-defined products in the crystalline form, derived from atom and group transfer to seven-coordinate iron, the collective data provide a starting point for the exploration of high-valent and metal-ligand multiply bonded species supported by approximate pentagonal-type ligand fields.

AB - We present a new structurally determined seven-coordinate iron platform supported by the tris(2-picolyl)amine ligand 6,6′-(pyridin-2- ylmethylazanediyl)bis(methylene)bis(N-tert-butylpicolinamide) (TPA 2C(O)NHtBu, 3) and its reactivity with oxo and nitrene transfer agents. Oxidation of the pentagonal bipyramidal, seven-coordinate iron(II)-triflate complex [TPA2C(O)NH tBuFeII(OTf)][OTf] (4) with PhIO produces the corresponding diiron(III) μ-oxo complex [(TPA2C(O)NH tBuFeIII)2(O)][OTf]4 (5). Mössbauer and magnetic measurements on 5 in the solid-state establish antiferromagnetic coupling between its two Fe(III) centers. Reactions of 4 with the nitrene transfer agents PhINTs (Ts = p-MeC6H4SO 2) and PhINNs (Ns = p-NO2C6H4SO 2) provide the corresponding iron(III)-amide congeners [TPA 2C(O)NHtBuFeIII(NHTs)][OTf] 2 (6) and [TPA2C(O)NHtBuFe III(NHNs)][OTf]2 (7), respectively, affording a rare pair of isolable Fe(III)-amide compounds formed from nitrene transfer. By characterizing well-defined products in the crystalline form, derived from atom and group transfer to seven-coordinate iron, the collective data provide a starting point for the exploration of high-valent and metal-ligand multiply bonded species supported by approximate pentagonal-type ligand fields.

KW - High-spin iron

KW - Mössbauer spectroscopy

KW - Oxo and nitrene transfer

KW - Pentagonal bipyramidal

KW - Seven-coordinate

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U2 - 10.1016/j.ica.2010.12.040

DO - 10.1016/j.ica.2010.12.040

M3 - Article

AN - SCOPUS:79953855278

SN - 0020-1693

VL - 369

SP - 82

EP - 91

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 1

ER -

A seven-coordinate iron platform and its oxo and nitrene reactivity

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Keywords

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