Oxidative atom-transfer to a trimanganese complex to form Mn 6(μ 6-E) (E = O, N) clusters featuring interstitial oxide and nitride functionalities

Alison R. Fout; Qinliang Zhao; Dianne J. Xiao; Theodore A. Betley

doi:10.1021/ja2066384

Oxidative atom-transfer to a trimanganese complex to form Mn ₆(μ ⁶-E) (E = O, N) clusters featuring interstitial oxide and nitride functionalities

Alison R. Fout, Qinliang Zhao, Dianne J. Xiao, Theodore A. Betley

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

Abstract

Utilizing a hexadentate ligand platform, a trinuclear manganese complex of the type ( ^HL)Mn ₃(thf) ₃ was synthesized and characterized ([ ^HL] ^6- = [MeC(CH ₂N(C ₆H ₄-o-NH)) ₃] ^6-). The pale-orange, formally divalent trimanganese complex rapidly reacts with O-atom transfer reagents to afford the μ ⁶-oxo complex ( ^HL) ₂Mn ₆(μ ⁶-O)(NCMe) ₄, where two trinuclear subunits bind the central O-atom and the ( ^HL) ligands cooperatively bind both trinuclear subunits. The trimanganese complex ( ^HL)Mn ₃(thf) ₃ rapidly consumes inorganic azide ([N ₃]NBu ₄) to afford a dianionic hexanuclear nitride complex [( ^HL) ₂Mn ₆(μ ⁶-N)](NBu ₄) ₂, which subsequently can be oxidized with elemental iodine to ( ^HL) ₂Mn ₆(μ ⁶-N)(NCMe) ₄. EPR and alkylation of the interstitial light atom substituent were used to distinguish the nitride from the oxo complex. The oxo and oxidized nitride complexes give rise to well-defined Mn(II) and Mn(III) sites, determined by bond valence summation, while the dianionic nitride shows a more symmetric complex, giving rise to indistinguishable ion oxidation states based on crystal structure bond metrics.

Original language	English (US)
Pages (from-to)	16750-16753
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	133
Issue number	42
DOIs	https://doi.org/10.1021/ja2066384
State	Published - Oct 26 2011
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja2066384

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@article{8ce8fe75c91845d8afb56cfa9d4efee8,

title = "Oxidative atom-transfer to a trimanganese complex to form Mn 6(μ 6-E) (E = O, N) clusters featuring interstitial oxide and nitride functionalities",

abstract = "Utilizing a hexadentate ligand platform, a trinuclear manganese complex of the type ( HL)Mn 3(thf) 3 was synthesized and characterized ([ HL] 6- = [MeC(CH 2N(C 6H 4-o-NH)) 3] 6-). The pale-orange, formally divalent trimanganese complex rapidly reacts with O-atom transfer reagents to afford the μ 6-oxo complex ( HL) 2Mn 6(μ 6-O)(NCMe) 4, where two trinuclear subunits bind the central O-atom and the ( HL) ligands cooperatively bind both trinuclear subunits. The trimanganese complex ( HL)Mn 3(thf) 3 rapidly consumes inorganic azide ([N 3]NBu 4) to afford a dianionic hexanuclear nitride complex [( HL) 2Mn 6(μ 6-N)](NBu 4) 2, which subsequently can be oxidized with elemental iodine to ( HL) 2Mn 6(μ 6-N)(NCMe) 4. EPR and alkylation of the interstitial light atom substituent were used to distinguish the nitride from the oxo complex. The oxo and oxidized nitride complexes give rise to well-defined Mn(II) and Mn(III) sites, determined by bond valence summation, while the dianionic nitride shows a more symmetric complex, giving rise to indistinguishable ion oxidation states based on crystal structure bond metrics.",

author = "Fout, {Alison R.} and Qinliang Zhao and Xiao, {Dianne J.} and Betley, {Theodore A.}",

year = "2011",

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T1 - Oxidative atom-transfer to a trimanganese complex to form Mn 6(μ 6-E) (E = O, N) clusters featuring interstitial oxide and nitride functionalities

AU - Fout, Alison R.

AU - Zhao, Qinliang

AU - Xiao, Dianne J.

AU - Betley, Theodore A.

PY - 2011/10/26

Y1 - 2011/10/26

N2 - Utilizing a hexadentate ligand platform, a trinuclear manganese complex of the type ( HL)Mn 3(thf) 3 was synthesized and characterized ([ HL] 6- = [MeC(CH 2N(C 6H 4-o-NH)) 3] 6-). The pale-orange, formally divalent trimanganese complex rapidly reacts with O-atom transfer reagents to afford the μ 6-oxo complex ( HL) 2Mn 6(μ 6-O)(NCMe) 4, where two trinuclear subunits bind the central O-atom and the ( HL) ligands cooperatively bind both trinuclear subunits. The trimanganese complex ( HL)Mn 3(thf) 3 rapidly consumes inorganic azide ([N 3]NBu 4) to afford a dianionic hexanuclear nitride complex [( HL) 2Mn 6(μ 6-N)](NBu 4) 2, which subsequently can be oxidized with elemental iodine to ( HL) 2Mn 6(μ 6-N)(NCMe) 4. EPR and alkylation of the interstitial light atom substituent were used to distinguish the nitride from the oxo complex. The oxo and oxidized nitride complexes give rise to well-defined Mn(II) and Mn(III) sites, determined by bond valence summation, while the dianionic nitride shows a more symmetric complex, giving rise to indistinguishable ion oxidation states based on crystal structure bond metrics.

AB - Utilizing a hexadentate ligand platform, a trinuclear manganese complex of the type ( HL)Mn 3(thf) 3 was synthesized and characterized ([ HL] 6- = [MeC(CH 2N(C 6H 4-o-NH)) 3] 6-). The pale-orange, formally divalent trimanganese complex rapidly reacts with O-atom transfer reagents to afford the μ 6-oxo complex ( HL) 2Mn 6(μ 6-O)(NCMe) 4, where two trinuclear subunits bind the central O-atom and the ( HL) ligands cooperatively bind both trinuclear subunits. The trimanganese complex ( HL)Mn 3(thf) 3 rapidly consumes inorganic azide ([N 3]NBu 4) to afford a dianionic hexanuclear nitride complex [( HL) 2Mn 6(μ 6-N)](NBu 4) 2, which subsequently can be oxidized with elemental iodine to ( HL) 2Mn 6(μ 6-N)(NCMe) 4. EPR and alkylation of the interstitial light atom substituent were used to distinguish the nitride from the oxo complex. The oxo and oxidized nitride complexes give rise to well-defined Mn(II) and Mn(III) sites, determined by bond valence summation, while the dianionic nitride shows a more symmetric complex, giving rise to indistinguishable ion oxidation states based on crystal structure bond metrics.

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