Multi-site reactivity: Reduction of six equivalents of nitrite to give an Fe 6(NO) 6 cluster with a dramatically expanded octahedral core

T. David Harris; Theodore A. Betley

doi:10.1021/ja2052655

Multi-site reactivity: Reduction of six equivalents of nitrite to give an Fe ₆(NO) ₆ cluster with a dramatically expanded octahedral core

T. David Harris, Theodore A. Betley^*

^*Corresponding author for this work

Chemistry

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

27 Scopus citations

Abstract

Reaction of NO ₂ ^- with the octahedral cluster ( ^HL) ₂Fe ₆ in the presence of a proton source affords the hexanitrosyl cluster ( ^HL) ₂Fe ₆(NO) ₆. This species forms via a proton-induced reduction of six nitrite molecules per cluster, utilizing each site available on the polynuclear core. Formation of the hexanitrosyl cluster is accompanied by a near 2-fold expansion of the ( ^HL) ₂Fe ₆ core volume, where intracore Fe-Fe interactions are overcome by strong π-bonding between Fe centers and NO ligands. A core volume of this magnitude is rare in octahedral metal clusters not supported by interstitial atoms. Moreover, the structural flexibility afforded by the ( ^HL) ₂Fe ₆ platform highlights the potential for other reaction chemistry involving species with metal-ligand multiple bonds. Carrying out the reaction of the cluster [( ^HL) ₂Fe ₆(NCMe) ₆] ⁴⁺ with nitrite in the absence of a proton source serves to forestall the nitrite reduction and enables clean isolation of the intermediate hexanitro cluster [( ^HL) ₂Fe ₆(NO ₂) ₆] ^2-.

Original language	English (US)
Pages (from-to)	13852-13855
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	133
Issue number	35
DOIs	https://doi.org/10.1021/ja2052655
State	Published - Sep 7 2011

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/ja2052655

Cite this

@article{68af792404594584983f40c0b2a49dc6,

title = "Multi-site reactivity: Reduction of six equivalents of nitrite to give an Fe 6(NO) 6 cluster with a dramatically expanded octahedral core",

abstract = "Reaction of NO 2 - with the octahedral cluster ( HL) 2Fe 6 in the presence of a proton source affords the hexanitrosyl cluster ( HL) 2Fe 6(NO) 6. This species forms via a proton-induced reduction of six nitrite molecules per cluster, utilizing each site available on the polynuclear core. Formation of the hexanitrosyl cluster is accompanied by a near 2-fold expansion of the ( HL) 2Fe 6 core volume, where intracore Fe-Fe interactions are overcome by strong π-bonding between Fe centers and NO ligands. A core volume of this magnitude is rare in octahedral metal clusters not supported by interstitial atoms. Moreover, the structural flexibility afforded by the ( HL) 2Fe 6 platform highlights the potential for other reaction chemistry involving species with metal-ligand multiple bonds. Carrying out the reaction of the cluster [( HL) 2Fe 6(NCMe) 6] 4+ with nitrite in the absence of a proton source serves to forestall the nitrite reduction and enables clean isolation of the intermediate hexanitro cluster [( HL) 2Fe 6(NO 2) 6] 2-.",

author = "Harris, {T. David} and Betley, {Theodore A.}",

year = "2011",

month = sep,

day = "7",

doi = "10.1021/ja2052655",

language = "English (US)",

volume = "133",

pages = "13852--13855",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "35",

}

TY - JOUR

T1 - Multi-site reactivity

T2 - Reduction of six equivalents of nitrite to give an Fe 6(NO) 6 cluster with a dramatically expanded octahedral core

AU - Harris, T. David

AU - Betley, Theodore A.

PY - 2011/9/7

Y1 - 2011/9/7

N2 - Reaction of NO 2 - with the octahedral cluster ( HL) 2Fe 6 in the presence of a proton source affords the hexanitrosyl cluster ( HL) 2Fe 6(NO) 6. This species forms via a proton-induced reduction of six nitrite molecules per cluster, utilizing each site available on the polynuclear core. Formation of the hexanitrosyl cluster is accompanied by a near 2-fold expansion of the ( HL) 2Fe 6 core volume, where intracore Fe-Fe interactions are overcome by strong π-bonding between Fe centers and NO ligands. A core volume of this magnitude is rare in octahedral metal clusters not supported by interstitial atoms. Moreover, the structural flexibility afforded by the ( HL) 2Fe 6 platform highlights the potential for other reaction chemistry involving species with metal-ligand multiple bonds. Carrying out the reaction of the cluster [( HL) 2Fe 6(NCMe) 6] 4+ with nitrite in the absence of a proton source serves to forestall the nitrite reduction and enables clean isolation of the intermediate hexanitro cluster [( HL) 2Fe 6(NO 2) 6] 2-.

AB - Reaction of NO 2 - with the octahedral cluster ( HL) 2Fe 6 in the presence of a proton source affords the hexanitrosyl cluster ( HL) 2Fe 6(NO) 6. This species forms via a proton-induced reduction of six nitrite molecules per cluster, utilizing each site available on the polynuclear core. Formation of the hexanitrosyl cluster is accompanied by a near 2-fold expansion of the ( HL) 2Fe 6 core volume, where intracore Fe-Fe interactions are overcome by strong π-bonding between Fe centers and NO ligands. A core volume of this magnitude is rare in octahedral metal clusters not supported by interstitial atoms. Moreover, the structural flexibility afforded by the ( HL) 2Fe 6 platform highlights the potential for other reaction chemistry involving species with metal-ligand multiple bonds. Carrying out the reaction of the cluster [( HL) 2Fe 6(NCMe) 6] 4+ with nitrite in the absence of a proton source serves to forestall the nitrite reduction and enables clean isolation of the intermediate hexanitro cluster [( HL) 2Fe 6(NO 2) 6] 2-.

UR - http://www.scopus.com/inward/record.url?scp=80052307965&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=80052307965&partnerID=8YFLogxK

U2 - 10.1021/ja2052655

DO - 10.1021/ja2052655

M3 - Article

C2 - 21815671

AN - SCOPUS:80052307965

SN - 0002-7863

VL - 133

SP - 13852

EP - 13855

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 35

ER -

Multi-site reactivity: Reduction of six equivalents of nitrite to give an Fe ₆(NO) ₆ cluster with a dramatically expanded octahedral core

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this